Polysiloxane-modified polyhydroxy polyurethane resin, method for producing same, heat-sensitive recording material using the resin, imitation leather, thermoplastic polyolefin resin skin material, material for weather strip, and weather strip

ABSTRACT

Disclosed are a polysiloxane-modified polyhydroxy polyurethane resin characterized by being derived from a reaction between a 5-membered cyclic carbonate polysiloxane compound represented by the below-described formula (1) and an amine compound, and its production process; and a resin composition, thermal recording medium, imitation leather, thermoplastic polyolefin resin skin material, weather strip material, and weather strip, all of which make use of the resin. 
     
       
         
         
             
             
         
       
     
     wherein A means

TECHNICAL FIELD

This invention relates to a novel polysiloxane-modified polyhydroxypolyurethane resin and its production process, and further, toutilization technologies of the resin. More specifically, this inventionis concerned with the provision of a novel polysiloxane-modifiedpolyhydroxy polyurethane resin, which is excellent in properties such aslubricity, abrasion resistance, chemical resistance, non-tackiness,antistatic properties and heat resistance and is useful as a rawmaterial for film and molding materials, various coating materials andvarious binders, and also with utilization technologies of the resin.This invention also pertains to technologies for the provision ofenvironment-responsive products, because the resin can use carbondioxide as its production raw material and can hence bring aboutreduction effect on carbon dioxide which has become problematic on aglobal scale.

As its specific application embodiments, the following embodiments canbe mentioned.

(1) A thermal recording medium, which is provided on a back side thereofwith a heat-resistant protective layer formed of thepolysiloxane-modified polyhydroxy polyurethane resin and which is usefulin thermal fusion transfer recording methods and thermal sublimationtransfer recording methods.

(2) An imitation leather, which can be obtained by using a compositioncontaining the polysiloxane-modified polyhydroxy polyurethane resin as aprincipal component and which is excellent in hand feeling, lubricity,scratch resistance, abrasion resistance and chemical resistance.

(3) A skin material made of a thermoplastic polyolefin resin, which usesthe polysiloxane-modified polyhydroxy polyurethane resin for theformation of a top coat layer, is useful in a car interior trimmaterial, home electric appliance component or part, or the like, andcan form a film a surface of which is excellent in lubricity, surfacetouch feeling, scratch resistance, abrasion resistance, chemicalresistance and uniform matting effect.

(4) A weather strip, which employs a high-molecular elastomer materialas a base material and uses the polysiloxane-modified polyhydroxypolyurethane resin in a surface treatment layer formed at a slidecontact portion, where the weather strip is to be brought into slidingcontact with another part, to provide the surface treatment layer withexcellent lubricity, abrasion resistance, heat resistance andweatherability.

BACKGROUND ART

Polyhydroxy polyurethane resins, which make use of carbon dioxide as araw material, are known for some time as reported in Non-patentDocuments 1 and 2. Under the current situation, however, the developmentof their applications has not moved ahead, because the above-described,conventionally-known resins are evidently inferior in characteristics topolyurethane-based resins as conventional, fossil-based high-molecularcompounds (fossil-based plastics) (see Patent Documents 1 and 2).

However, the global warming phenomenon which can be considered to beattributable to the ever-increasing emission of carbon dioxide hasbecome a worldwide problem in recent years, and a reduction in carbondioxide emissions has arisen as a critical issue for the entire world sothat there is an outstanding desire for a technology that makes itpossible to use carbon dioxide as a production raw material. The changeto renewable resources such as biomass and methane has also become aworldwide trend from the viewpoint of the problem of exhaustible fossilresources (petroleum).

Under such a background as described above, polyhydroxy polyurethaneresins are drawing a fresh look again. Described specifically, carbondioxide which is a raw material for these resins is a readily-availableand sustainable carbon resource, and moreover, plastics that make use ofcarbon dioxide as a replacement for fossil resources can be consideredto be an effective means for resolving problems such as theabove-described warming and resource depletion.

It is, therefore, very preferable from the foregoing situation torealize the above-described replacement to polyhydroxy polyurethaneresins, which can use carbon dioxide as a production raw material, invarious applications where polyurethane-based resins as conventionalfossil-based high-molecular compounds (fossil-based plastics) are used.Nonetheless, the conventional polyhydroxy polyurethane resins areinferior in characteristics to the fossil-based plastics as mentionedabove. To spur the development of their applications, it is, therefore,essential to take into full consideration the circumstances in therespective applications and the performances suited for them and todevelop resins capable of meeting these issues or requirements. Adescription will hereinafter be made about the conventional technologiesin the respective applications.

(Thermal Recoding Media)

Conventionally-known thermal recording media include thermal fusiontransfer recording media and thermal sublimation transfer recordingmedia. In each thermal fusion transfer recording medium, a thermalrecording layer (ink layer) is formed with a dye or pigment carried in abinder resin or the like on one side of a base sheet such as a polyesterfilm, and from the back side of the base sheet, heat is applied in apattern to transfer the ink layer onto a receiving medium. In eachthermal sublimation transfer recording medium, on the other hand, a heatsublimation dye is used as a dye, and the dye alone is allowed tosublime such that it is likewise transferred onto a receiving medium.

These methods both employ the principle that thermal energy is appliedby a thermal head from the back side of a base sheet, and therefore, theback side of the base sheet of a thermal recording medium to be used isrequired to have sufficient lubricity, separability, non-tackiness andthe like with respect to the thermal head and the thermal head is alsorequired not to stick to the back side (sticking phenomenon).Accordingly, there has been proposed, for example, a technology thatforms a back side layer of a silicone resin, melamine resin, phenolresin, polyimide resin, modified cellulose resin or a mixture thereof onthe back side of a base material sheet in a thermal recording medium(see Patent Document 3).

To form a heat-resistant protective layer on the above-described thermalrecording medium with a view to providing its back side with heatresistance, attempts have been made, for example, to use variouscrosslinking agents in the above-described resins to thermally crosslinkthem or to add inorganic fillers, fluorinated resin powders or the liketo these resins. These attempts can provide heat resistance, but areinsufficient as measures for improving the lubricity and non-tackinessto a thermal head. Only the silicone resin out of the above-describedresins is equipped with lubricity and non-tackiness, but this resininvolves another problem in that damage is given to the base sheet,which is generally a thin film of from 2 to 5 μm thickness, in a heatingstep conducted to completely crosslink the resin. When the thermalrecording medium is incompletely crosslinked to protect the base sheetfrom damage, on the other hand, the winding of the thermal recordingmedium into a roll form allows an unreacted, low-molecular silicone inthe heat-resistant protective layer, which is formed on the back side ofthe base sheet, to migrate into the ink layer located in contact withthe surface of the heat-resistant protective layer. As a result, aproblem arises such that an image formed with such a thermal recordingmedium is unclear.

It is also known to use a silicone-acrylic graft or block copolymer inthe heat-resistant protective layer. When a thermal recording medium isproduced by this method, however, the heat resistance can be improved alittle but the film-forming property of the acrylic component isinsufficient so that the heat-resistant protective layer may separatefrom the base material. Moreover, this method is accompanied by adrawback that the heat-resistant protective layer is prone to abrasionand worn-out fragments of the protective layer deposit on a thermalhead, thereby inducing new problems such as poor traveling and poorprinting of the thermal recording medium and a reduced service life ofthe thermal head.

The present inventors studied on methods for solving these variousproblems, and proposed that the use of various silicone polyurethanecopolymer resins makes it possible to obtain thermal recording mediahaving a heat-resistant protective layer equipped with heat resistance,slidability, non-tackiness and the like in combination (see PatentDocuments 4 to 6). These proposals were, however, not studied from theviewpoint of the preservation of the global environment, which hasbecome a worldwide issue in recent years. It is, therefore, desired toreview these technologies from such a new viewpoint.

(Imitation Leathers)

Conventionally, imitation leathers have been used in pouches, bags,shoes, furniture, clothing, vehicle interior trim materials, electricappliances, and the like. As resins for these imitation leathers,polyurethane-based resins are widely used. The term “imitation leather”is a generic term for leather-like products manufactured resemblingnatural leathers. In general, imitation leathers can be roughly dividedinto artificial leathers, synthetic leathers, and vinyl chlorideleathers.

Artificial leathers have a structure closest to that of natural leathersamong imitation leathers, and use a non-woven fabric as a base fabric.As a process for the production of a general artificial leather, thereis a process to be described hereinafter. After a nonwoven fabric isfirst impregnated with a solution of a polyurethane-based resin indimethylformamide (hereinafter, DMF), the polyurethane-based resin issolidified and dried into a porous form by wet-process film formation(submerged solidification). Subsequently, its surface is further coatedwith a polyurethane-based resin or provided with a laminated layer ofthe polyurethane-based resin to present a smooth tone, or its surface isground to raise fibers such that a suede tone is presented.

On the other hand, synthetic leathers use, as a base fabric, a fabricsuch as a woven fabric or raised blanket, and in general, are roughlydivided into dry-process synthetic leathers and wet-process syntheticleathers. For the production of a dry-process synthetic leather, thereare two processes, one being to coat a polyurethane-based resin directlyon a base fabric and to dry it, and the other to coat apolyurethane-based resin on a sheet of release paper, to dry thepolyurethane-based resin into a film, and then to bond the film and abase fabric together with an adhesive. On the other hand, a wet-processsynthetic leather can be produced by impregnating or coating a basefabric with the above-mentioned solution of the polyurethane-based resinin DMF and then subjecting the polyurethane-based resin to submergedsolidification and drying to form a porous layer. Further, the surfaceof the synthetic leather obtained by the dry process or wet process asdescribed above is coated with a polyurethane-based resin or providedwith a laminated layer of the polyurethane-based resin to present asmooth tone, or the surface is ground to raise fibers such that a suedetone is presented.

There is an increasing consciousness towards the preservation of theglobal environment in recent years. The change to renewable resourcessuch as biomass and methane has become a worldwide trend from theviewpoint of the problem of exhaustible fossil resources (petroleum).Under such a background, more and more makers are also positivelyworking on environmental measures in the field of imitation leatherproducts in recent years, resulting in a move toward forming imitationleather products by using materials excellent in environmentalpreservation properties. A great deal of research is hence under way,for example, to reduce VOC (volatile organic compound) emissions as muchas possible by using as polyurethane-based resin those which aredispersible or emulsifiable in water-based media in place of organicsolvents or to use plant-derived raw materials from the viewpoint ofcarbon neutral (Patent Documents 7 to 9). However, the resultingimitation leather products are still different in performance comparedwith the conventional products, and therefore, are considered to haveproblems for practical applications. Moreover, these approaches arestill insufficient in respect to the solution of new environmentalproblems such as the reduction of carbon dioxide emissions, which hasbecome a critical worldwide issue.

(Skin Materials Made of Thermoplastic Polyolefin Resins)

The recycling of vehicle interior trim materials (instrument panels,door trims, etc.) and home electric appliance components and parts isstrongly desired to decrease waste materials as much as possible afteruse in view of the garbage-related problems and environment-relatedproblems in recent years. From this viewpoint, thermoplasticpolyolefins, for example, polypropylene (PP), ABS resin, AS resin,polyolefin-based thermoplastic elastomers (TPO) and the like are used asskin materials for vehicle interior trim materials and home electricappliance components and parts in recent years. However, thesethermoplastic polyolefins are inferior in surface adhesiveness, scratchresistance, abrasion resistance and chemical resistance in comparisonwith vinyl chloride resin and the like which have been conventionallyused, and therefore, are required to apply coatings in order to improvethem in these properties. It is also necessary to provide artistry forgiving a high-grade appearance, and especially in the case of carinterior trim materials, to consider not only artistry but also anattention to anti-glare properties for drivers and like properties. Itis, therefore, a current practice to apply various coatings tothermoplastic polyolefin base materials such that top coat layers areformed to impart a function to their surfaces for the provision of stillbetter skin materials.

In the coating formulations to be employed as described above, thebelow-described resins and the like are used, and a variety of studieshave been made on such resins. Proposals have been made including, forexample, a method that employs a coating formulation making use of achlorinated polypropylene-modified acrylic resin, which has goodadhesiveness to polyolefin-based resins such as PP resin and TPO resin,as a binder and containing a matting agent such as an inorganic extenderpigment (silica or talc) or acrylic resin particles added thereto and amethod that applies a chlorinated polypropylene-based primer and thenapplies on the primer a coating formulation containing a polyester resinor polyurethane resin.

There is an increasing consciousness towards the preservation of theglobal environment in recent years. The change to renewable resourcessuch as biomass and methane has become a worldwide trend from theviewpoint of the problem of exhaustible fossil resources (petroleum).Under such a situation, more and more makers are also positively workingon environmental measures in the field of the above-descried skinmaterials made of thermoplastic polyolefin resins in recent years,resulting in a move toward forming such products by using materialsexcellent in environmental preservation properties. A great deal ofresearch is hence under way, for example, to avoid choosing specificsolvents (toluene and the like) from organic solvents for use in theabove-described coating formulations or to use water-based resinsinstead of organic solvents for reducing VOC (volatile organic compound)emissions as much as possible (Patent Documents 10 to 12). However,these approaches are also still insufficient in respect to the solutionof new environmental problems such as the reduction of carbon dioxideemissions, which has become a critical worldwide issue.

(Weather Strip Materials)

As materials for forming weather strips such as glass runs, door weatherstrips, body side weather strips, inside seals and outside seals in carsand buildings, high-molecular elastomer materials such as chloroprenerubber, styrene-butadiene rubber, nitrile rubber and EPDM rubber havebeen used conventionally. It is a common practice to form surfacetreatment layers on the surfaces of these weather strips by a methodsuch as coating or impregnation such that performance such as lubricity,abrasion resistance, mold release properties, heat resistance, waterresistance and weatherability can be imparted.

As materials for forming such surface treatment layers, a variety ofcoating formulations have been proposed including one containing athermosetting polyurethane resin and a silicone oil added thereto (seePatent Document 13), one containing a thermosetting polyurethane resinand an organopolysiloxane added thereto (see Patent Document 14), andone composed of a urethane prepolymer, a silicone oil, hydrophobicsilica and a polyisocyanate (see Patent Document 15).

On the other hand, there is an increasing consciousness towards thepreservation of the global environment in recent years. The change torenewable resources such as biomass and methane has become a worldwidetrend from the viewpoint of the problem of exhaustible fossil resources(petroleum). Under such a situation, more and more makers are positivelyworking on environmental measures, resulting in a move toward formingweather strips by using materials excellent in environmentalpreservation properties. A great deal of research is hence under way,for example, to avoid choosing specific solvents (toluene and the like)from organic solvents for use in the above-described coatingformulations or to use water-based resins instead of organic solventsfor reducing VOC (volatile organic compound) emissions as much aspossible (see Patent Document 16). However, these approaches are alsostill insufficient in respect to the solution of new environmentalproblems such as the reduction of carbon dioxide emissions, which hasbecome a critical worldwide issue.

PRIOR ART DOCUMENTS Non-patent Documents

-   Non-patent Document 1: N. Kihara, T. Endo, J. Org. Chem., 58, 6198    (1993)-   Non-patent Document 2: N. Kihara, T. Endo, J. Polymer Sci., Part A    Polymer Chem., 31(11), 2765 (1993)

Patent Documents

-   Patent Document 1: U.S. Pat. No. 3,072,613-   Patent Document 2: JP-A-2000-319504-   Patent Document 3: JP-A-58-13359-   Patent Document 4: JP-A-61-227087-   Patent Document 5: JP-A-62-202786-   Patent Document 6: JP-A-2-102096-   Patent Document 7: JP-A-2009-144313-   Patent Document 8: JP-A-2007-270373-   Patent Document 9: JP-A-2005-154580-   Patent Document 10: JP-A-2006-307015-   Patent Document 11: JP-A-2004-51901-   Patent Document 12: JP-A-2006-176615-   Patent Document 13: JP-A-56-4408-   Patent Document 14: JP-A-8-225670-   Patent Document 15: JP-A-8-109349-   Patent Document 16: JP-A-2008-56772

DISCLOSURE OF THE INVENTION Problem to be Solved by the Invention

As mentioned above, polyhydroxy polyurethane resins that make use ofcarbon dioxide as a production raw material are known for some years,but are inferior in performance. To use them for industrial applicationsas replacements for fossil-based plastics, they, however, need to beprovided with improved performance and a new additional value. Describedspecifically, also from the viewpoint of a reduction in carbon dioxideemissions, there is an outstanding desire for the development of a resinthat can further improve the performance indispensable for industrialapplications, such as heat resistance, chemical resistance and abrasionresistance. To apply the above-described resins for the above-mentionedrespective use, there are desires to be described below for therespective resins.

An object of the present invention is, therefore, to develop a novelresin, which can satisfy characteristics required for the respectiveapplications, can use carbon dioxide as a production raw material, andmoreover, can provide environment-responsive products also excellentfrom the viewpoint of the preservation of the global environment.

(Thermal Recording Media)

Keeping in step with the adoption of thermal heads of highertemperatures and base material sheets of smaller thicknesses as a resultof the move toward higher printing speeds in recent years, still higherheat resistance, lubricity and non-tackiness, a countermeasure againststatic electricity to be produced upon peeling a film, and the like arerequired for the heat-resistant protective layer on the backside. Inaddition, there is also a need for making improvements in the situationthat the conventional thermal recording media (materials) are hardlyrecyclable as valuable resources after use and have resulted in thegeneration of massive waste.

It is, therefore, required to develop a technology that can provide athermal recording medium as an environment-responsive product alsoexcellent from the viewpoint of the preservation of the globalenvironment although it has a heat-resistant protective layer excellentin heat resistance, slidability and non-tackiness.

(Imitation Leathers)

Concerning imitation leathers, it is desired to develop anenvironment-responsive product which has still higher pliability, isexcellent in surface lubricity, scratch resistance, abrasion resistanceand chemical resistance, and has environmental preservation propertieson a global scale.

(Skin Materials Made of Thermoplastic Polyolefin Resins)

In respect to skin materials made of thermoplastic polyolefin resins foruse in vehicle interior trim materials and home electric appliancecomponents and parts, it is desired to develop an environment-responsiveproduct which has still higher surface lubricity, scratch resistance,abrasion resistance and chemical resistance and if necessary, alsoexcellent uniform matting effect, and has environmental preservationproperties on a global scale.

It is, therefore, required to develop a technology capable of providinga skin material made of a thermoplastic polyolefin resin, which is askin material made of the thermoplastic polyolefin material and havingthe above-described excellent properties, and is also a superbenvironment-responsive product.

(Weather Strips)

It is very useful if a surface treatment layer to be arranged by amethod such as coating or impregnation on a weather strip for a car orbuilding can be formed as an environment-responsive product which isexcellent especially in basic properties such as lubricity, abrasionresistance, heat resistance and weatherability and has environmentalpreservation properties on a global scale.

There is, accordingly, a desire for a technology capable of providing amaterial, which is useful in forming a surface treatment layer at aslide contact portion of a high-molecular elastomer material making up aweather strip, said slide contact portion being to be brought intosliding contact with another part, and which can provide the resultingsurface treatment layer with excellent lubricity, abrasion resistance,heat resistance and weatherability although it is a materialcontributable to environmental preservation properties.

Means for Solving the Problem

The above-described object can be achieved by the present invention tobe described hereinafter. Specifically, the present invention provides apolysiloxane-modified polyhydroxy polyurethane resin characterized bybeing derived from a reaction between a 5-membered cyclic carbonatepolysiloxane compound represented by the following formula (1) and anamine compound:

wherein A means

in which R₁ means an alkylene group which has from 1 to 12 carbon atomsand may have therein a linkage by an element of O, S or N and/or alinkage by —(C₂H₄O)_(b)—, R₂ means a direct bond or an alkylene grouphaving from 2 to 20 carbon atoms, R₂ may be linked to an alicyclic groupor aromatic group, b stands for a number of from 1 to 300, and a standsfor a number of from 1 to 300.

The present invention also provides, as another embodiment, a processfor producing a polysiloxane-modified polyhydroxy polyurethane resin,which comprises deriving from a reaction between a 5-membered cycliccarbonate polysiloxane compound represented by the formula (1) and anamine compound. As its preferred embodiment, it is possible to mentionthe above-described process for producing the polysiloxane-modifiedpolyhydroxy polyurethane resin, wherein as the 5-membered cycliccarbonate polysiloxane compound, a 5-membered cyclic carbonatepolysiloxane compound obtained by reacting an epoxy-modifiedpolysiloxane compound represented by the following formula (2) withcarbon dioxide is used:

wherein A means

in which R₁ means an alkylene group which has from 1 to 12 carbon atomsand may have therein a linkage by an element of O, S or N and/or alinkage by —(C₂H₄O)_(b)—, R₂ means a direct bond or an alkylene grouphaving from 2 to 20 carbon atoms, R₂ may be linked to an alicyclic groupor aromatic group, b stands for a number of from 1 to 300, and a standsfor a number of from 1 to 300.

The present invention also provides a thermal recording medium having abase material sheet, a thermal recording layer arranged on at least oneside of the base material sheet, and a heat-resistant protective layerarranged on another side of the base material sheet, said another sidebeing a back side to be brought into contact with a thermal head,wherein the heat-resistant protective layer is formed with a resincomposition that comprises at least the above-describedpolysiloxane-modified polyhydroxy polyurethane resin.

The present invention also provides an imitation leather comprising abase fabric and a resin composition comprising as a principal componentthereof the above-described polysiloxane-modified polyhydroxypolyurethane resin and impregnated in or laminated on the base fabric.

The present invention also provides a skin material made of athermoplastic polyolefin resin, comprising a thermoplastic polyolefinresin sheet and a top coat layer formed directly or via a primer layeron the sheet, wherein the top coat layer comprises as a principalcomponent thereof the above-described polysiloxane-modified polyhydroxypolyurethane resin.

The present invention also provides a weather strip material for coatingand/or impregnating a high-molecular elastomer material to form asurface treatment layer at a slide contact portion to be brought intosliding contact with another part, comprising a resin composition whichcomprises the above-described polysiloxane-modified polyhydroxypolyurethane resin. The present invention also provides a weather stripcomprising a high-molecular elastomer material and the weather stripmaterial coated on and/or impregnated in the high-molecular elastomermaterial to form a surface treatment layer at a slide contact portion tobe brought into sliding contact with another part, wherein the surfacetreatment layer has been crosslinked with a crosslinking agent reactablewith hydroxyl groups in a structure of the polysiloxane-modifiedpolyhydroxy polyurethane resin in the weather strip material.

Advantageous Effects of the Invention

The polysiloxane-modified polyhydroxy polyurethane resin provided by thepresent invention can form a film excellent in lubricity, abrasionresistance, chemical resistance, non-tackiness, antistatic properties,heat resistance and the like, and can replace conventional fossil-basedplastics. As the resin provided by the present invention can use carbondioxide as a production raw material, the present invention makes itpossible to provide products which are responsive to the globalenvironment and can contribute to a reduction in carbon dioxide as agreenhouse gas. More specifically, the present invention can providevarious products to be described hereinafter.

(Thermal Recording Medium)

In the present invention, the formation of a heat-resistant protectivelayer with the polysiloxane-modified polyhydroxy polyurethane resin on aback side makes it possible to provide a thermal recording medium whichis excellent in the heat resistance, lubricity and non-tackiness of theheat-resistant protective layer, the adhesiveness of the heat-resistantprotective layer to a base sheet, and further, the antistatic effect andthe like of the heat-resistant protective layer. As the above-describedresin can provide such an excellent thermal recording medium and at thesame time, can use carbon dioxide as a raw material and can incorporatecarbon dioxide in the resin, it is possible to provide a thermalrecording medium also useful as an environment-responsive product thatcontributes to a reduction in greenhouse gas.

(Imitation Leather)

According to the present invention, there is provided an imitationleather having a hand feeling, which is no way inferior to those ofconventional imitation leather products, and is also provided withexcellent surface lubricity, scratch resistance, abrasion resistance andchemical resistance. In addition, the resin with carbon dioxideincorporated and fixed therein can be used as a material for forming theimitation leather. The imitation leather is provided as anenvironment-responsive product, which can also contribute to a reductionin carbon dioxide considered to be a worldwide problem as a greenhousegas, and is also excellent from the viewpoint of the preservation of theglobal environment.

(Skin Material Made of Thermoplastic Polyolefin Material)

In the present invention, the use of the specific polysiloxane-modifiedpolyhydroxy polyurethane resin as a material for forming a top coat,which makes up a skin material made of a thermoplastic polyolefinmaterial, makes it possible to provide the surface of the resulting skinmaterial with excellent lubricity, surface touch feeling, scratchresistance, abrasion resistance, chemical resistance, and if necessary,uniform matting effect. In addition, the resin with carbon dioxideincorporated and fixed therein can be used as a material for forming thetop coat layer, thereby making it possible to provide the skin materialmade of the thermoplastic polyolefin resin as an environment-responsiveproduct capable of also contributing to a reduction in carbon dioxidewhich is considered to be a worldwide problem as a greenhouse gas.

(Weather Strip)

According to the present invention, there is provided a useful materialfor forming a surface treatment layer at a slide contact portion of ahigh-molecular elastomer material as a base material in a weather stripfor a car or building, said slide contact portion being to be broughtinto sliding contact with another part. The material provides theresulting surface treatment layer with excellent lubricity, abrasionresistance, heat resistance and weatherability although it contributesto environmental preservation properties. More specifically, acomposition with the polysiloxane-modified polyhydroxy polyurethaneresin included therein is used as a coating formulation for the surfacetreatment of a high-molecular elastomer in the present invention, sothat the resulting surface treatment layer is excellent in theabove-described basic properties. Moreover, carbon dioxide which isconsidered to be a greenhouse gas can be used as its production rawmaterial, thereby making it possible to provide a material also usefulfrom the viewpoint of the preservation of the global environment andfurther, an environment-responsive product which makes use of thematerial.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an infrared absorption spectrum of an epoxy-modifiedpolysiloxane.

FIG. 2 is an infrared absorption spectrum of a 5-membered cycliccarbonate polysiloxane.

FIG. 3 shows a GPC elution curve of the 5-membered cyclic carbonatepolysiloxane (mobile phase: THF, column: “TSK-GELGMHXL+G2000HXL+G3000HXL”, detector: IR detector)

MODES FOR CARRYING OUT THE INVENTION

The present invention will next be described in further detail based onpreferred embodiments.

<Polysiloxane-Modified Polyhydroxy Polyurethane Resin>

The polysiloxane-modified polyhydroxy polyurethane resin according tothe present invention (which may hereinafter be called simply “the resinaccording to the present invention” or “the resin for use in the presentinvention”) is characterized by being derived from a reaction between a5-membered cyclic carbonate polysiloxane compound represented by thefollowing formula (1) and an amine compound:

wherein A means

in which R₁ means an alkylene group which has from 1 to 12 carbon atomsand may have therein a linkage by an element of O, S or N and/or alinkage by —(C₂H₄O)_(b)—, R₂ means a direct bond or an alkylene grouphaving from 2 to 20 carbon atoms, R₂ may be linked to an alicyclic groupor aromatic group, b stands for a number of from 1 to 300, and a standsfor a number of from 1 to 300.

On the other hand, this 5-membered cyclic carbonate polysiloxanecompound can be produced, for example, by reacting an epoxy-modifiedpolysiloxane compound with carbon dioxide as shown by thebelow-described “Equation-A”. Described more specifically, it can beobtained by reacting the epoxy-modified polysiloxane compound withcarbon dioxide in the presence or absence of an organic solvent, in thepresence of a catalyst, at a temperature of from 40° C. to 150° C.,under normal pressure or slightly elevated pressure, for from 10 to 20hours.

Examples of the epoxy-modified polysiloxane compound, which is usable inthe present invention, include such compounds as will be described next.

The above-listed epoxy-modified polysiloxane compounds are preferredcompounds for use in the present invention, and the present inventionshall not be limited to these exemplified compounds. Not only theabove-exemplified compounds but also other similar epoxy-modifiedpolysiloxane compounds are available on the market these days.Accordingly, those readily available on the market can all be used inthe present invention.

The 5-membered cyclic carbonate polysiloxane compound for use in thepresent invention can be obtained through the reaction between such anepoxy-modified polysiloxane compound as described above and carbondioxide. As catalysts usable in this reaction, base catalysts and Lewisacid catalysts can be mentioned. The base catalysts include tertiaryamines such as triethylamine and tributylamine; cyclic amines such asdiazabicycloundecene, diazabicyclooctane and pyridine; alkali metalsalts such as lithium chloride, lithium bromide, lithium fluoride andsodium chloride; alkaline earth metal salts such as calcium chloride;quaternary ammonium salts such as tetrabutyl ammonium chloride,tetraethyl ammonium bromide and benzyl trimethyl ammonium chloride;carbonate salts such as potassium carbonate and sodium carbonate; metalacetates such as zinc acetate, lead acetate, copper acetate and ironacetate; metal oxides such as calcium oxide, magnesium oxide and zincoxide; and phosphonium salts such as tetrabutyl phosphonium chloride.

The Lewis acid catalysts include tin compounds such as tetrabutyltin,dibutyltin dilaurate, dibutyltin diacetate and dibutyltin octoate.

Such a catalyst may be used in a proportion of from 0.1 to 100 parts bymass, preferably from 0.3 to 20 parts by mass per 50 parts by mass ofthe epoxy-modified polysiloxane compound. If the above-describedcatalyst is used in a proportion of smaller than 0.1 parts by mass, thecatalyst will be unable to fully exhibit its effects as a catalyst. Ifthe above-described catalyst is used in an unduly large proportion, onthe other hand, the resin to be obtained finally may be lowered invarious performance. Therefore, such an excessively small or largeproportion is not preferred. In such a case that the residual catalystwould induce a serious reduction in performance, however, the reactionmixture may be washed with purified water to remove the residualcatalyst.

Organic solvents usable in the reaction between the epoxy-modifiedpolysiloxane compound and carbon dioxide include, for example,dimethylformamide, dimethyl sulfoxide, dimethylacetamide,N-methylpyrrolidone, N-ethylpyrrolidone, tetrahydrofuran, and the like.These organic solvents may also be used as mixed systems with other poorsolvents, for example, methyl ethyl ketone, xylene, toluene,tetrahydrofuran, diethyl ether, cyclohexanone, and the like.

The resin according to the present invention can be obtained by reactingthe 5-membered cyclic carbonate polysiloxane compound, which has beenobtained, for example, through the above-described reaction, with anamine compound in the presence of an organic solvent at a temperature offrom 20° C. to 150° C. as shown by the below-described “Equation-B”.

As the amine compound for use in the above-described reaction, a diamineis preferred, for example. No particular limitation is imposed on thediamine, and diamines which have been conventionally used in theproduction of polyurethane resins are all usable. Illustrative arealiphatic diamines such as methylenediamine, ethylenediamine,trimethylenediamine, 1,3-diaminopropane, hexamethylenediamine andoctamethylenediamine; aromatic diamines such as phenylenediamine,3,3′-dichloro-4,4′-diaminodiphenylmethane,4,4′-methylenebis(phenylamine), 4,4′-diaminodiphenyl ether,4,4′-diaminodiphenylsulfone, meta-xylylenediamine andpara-xylylenediamine; alicyclic diamines such as 1,4-cyclohexanediamine,4,4′-diaminocyclohexylmethane, 1,4′-diaminomethylcyclohexane andisophorone diamine; and alkanoldiamines such as monoethanoldiamine,ethylaminoethanolamine and hydroxyethylaminopropylamine. Other diaminesare also available on the market these days. These diamine compoundsreadily available from the market can all be used in the presentinvention.

In the polysiloxane-modified polyhydroxy polyurethane resin according tothe present invention obtained as described above, the percentage ofpolysiloxane segments in the resin may preferably be from 1 to 75 mass %in terms of the content of the segments based on the molecule of theresin. Described specifically, a percentage of smaller than 1 mass %leads to insufficient development of a function associated with surfaceenergy based on the polysiloxane segments, and therefore, is notpreferred. On the other hand, a percentage of higher than 75 mass %provides the polyhydroxy urethane resin with insufficient performance inmechanical strength, abrasion resistance and the like. The percentage ofpolysiloxane segments may be more preferably from 2 to 60 mass %, stillmore preferably from 5 to 30 mass %.

The resin according to the present invention may preferably have anumber average molecular weight (a polystyrene-equivalent value asmeasured by GPC) of from 2,000 to 100,000 or so. Further, one having anumber average molecular weight of from 5,000 to 70,000 or so is morepreferred.

The resin according to the present invention is derived from thereaction between the above-described 5-membered cyclic carbonatepolysiloxane compound represented by the formula (1) and the aminecompound. Hydroxyl groups which are formed by the reaction of the5-membered cyclic carbonate groups in the structure of the resin withthe amine compound can, therefore, bring about further improvements inperformance. Described specifically, these hydroxyl groups havehydrophilicity and therefore, can significantly improve the adhesivenessof the resin to the base material and can also obtain antistatic effectwhich is unavailable from conventional products. Furthermore, the use ofa reaction between the hydroxyl groups in the structure of the resin anda crosslinking agent or the like added to the resin can achieve furtherimprovements in heat resistance, abrasion resistance, chemicalresistance and the like, and is suitable, for example, when a surfacetreatment layer or the like is formed.

The hydroxyl value of the resin according to the present invention maypreferably be from 20 to 300 mgKOH/g. If the hydroxyl content is smallerthan the above-described range, the carbon dioxide reduction effect ishardly considered to be available sufficiently. If the hydroxyl valueexceeds the above-described range, various physical properties as a highmolecular compound, such as mechanical/physical properties, becomeinsufficient.

The polysiloxane-modified polyhydroxy polyurethane resin provided by thepresent invention can be used as a resin crosslinked with a crosslinkingagent, although it can be used as it is. As the crosslinking agentusable as described above, any crosslinking agent can be also usedinsofar as it reacts with the hydroxyl groups in the resin structure.Examples include alkyl titanate compounds and polyisocyanate compounds.No particular limitation is imposed on these polyisocyanate compoundsinsofar as they are known and have been conventionally used in thecrosslinking of polyurethane resins. Illustrative are adducts or thelike of polyisocyanates, which have such structural formulas as will bedescribed below, with other compounds.

When the resin according to the present invention is used for variousapplications, for example, for the formation of a film, any desired oneor more of conventionally-known various binder resins can be used ormixed, for example, to provide improved coating applicability to thebase material and improved film-forming property or to adjust thecontent of polysiloxane segments. As the binder resin or resins to beused as described above, those chemically reactable with a crosslinkingagent such as the above-described polyisocyanate adduct or the like arepreferred, although even those having no reactivity can be also used.

As resins to be used as described above, various resins which have beenconventionally employed as binders can be used, and no particularlimitation is imposed. Usable examples include acrylic resins,polyurethane resins, polyester resins, polybutadiene resins, siliconeresins, melamine resins, phenol resins, polyvinyl chloride resins,cellulose resins, alkyd resins, modified cellulose resins, fluorinatedresins, polyvinyl butyral resins, epoxy resins, polyamide resins, andthe like. It is also possible to use resins obtained by modifying theabove-described resins with silicone or fluorine. When a binder resin isused in combination, it may be used or added in a proportion ofpreferably from 5 to 90 parts by mass, more preferably from 10 to 60parts by mass or so per 100 parts by mass of the polysiloxane-modifiedpolyhydroxy polyurethane resin according to the present invention.

When the resin according to the present invention is formed, forexample, into a film, the polysiloxane segments in the structure of theresin orient in a surface of the film so that the film is provided withheat resistance, lubricity and non-tackiness all of which arecharacteristics of polysiloxane segments. In addition, the hydroxylgroups in the structure of the resin strongly interact with the basematerial, on which the film has been formed, at the interface betweenthem, so that the film is provided with excellent adhesiveness to thebase material, superb flexibility and outstanding antistatic effect.Therefore, the use of the resin according to the present invention makesit possible to obtain a product of excellent performance. Further, the5-membered cyclic carbonate polysiloxane compound that makes up theresin according to the present invention can incorporate carbon dioxidein the resin owing to the use of carbon dioxide as a production rawmaterial. The present invention can, therefore, provide anenvironment-responsive material, which is also useful from the viewpointof a reduction in carbon dioxide considered to be a cause of globalwarming and which is unavailable from conventional products.

As has been described above, the polysiloxane-modified polyhydroxypolyurethane resin according to the present invention is very useful asvarious molding materials, materials for synthetic leathers andartificial leathers, fiber coating materials, surface treatmentmaterials, thermal recording media, strippable materials, paints,binders for printing inks, and the like, and its applications areexpected to be promising. A specific description will hereinafter bemade about various products that make use of the polysiloxane-modifiedpolyhydroxy polyurethane resin according to the present invention.

<Thermal Recording Medium>

In the thermal recording medium according to the present invention, thethermal recording layer is arranged on at least one side of the basematerial sheet, and the heat-resistant protective layer is formed on theother side, i.e., the back side of the base material sheet. The thermalrecording medium according to the present invention is characterized inthat the high-molecular compound, which makes up the heat-resistantprotective layer, is the above-described polysiloxane-modifiedpolyhydroxy polyurethane resin. Described specifically, the thermalrecording medium according to the present invention is characterized inthat the heat-resistant protective layer is formed of thepolysiloxane-modified polyhydroxy polyurethane resin of the presentinvention, which has been derived from the reaction between the5-membered cyclic carbonate polysiloxane compound represented by theformula (1) and the amine compound, or is formed of a resin compositioncontaining the resin.

The heat-resistant protective layer, which makes up the thermalrecording medium according to the present invention, can be formed as afilm composed of the above-described polysiloxane-modified polyhydroxypolyurethane resin. Using a crosslinking agent, the film can also beprovided as a crosslinked film. As the crosslinking agent usable asdescribed above, any crosslinking agent can be used insofar as it reactswith the hydroxyl groups in the resin structure. Examples include alkyltitanate compounds and polyisocyanate compounds. No particularlimitation is imposed on these polyisocyanate compounds insofar as theyare known and have been conventionally used in the crosslinking ofpolyurethane resins. Illustrative are adducts or the like ofpolyisocyanates, which have such structural formulas as described above,with other compounds.

Upon forming the heat-resistant protective layer on the back side of thebase material sheet to form the thermal recording medium according tothe present invention, any desired one or more of conventionally-knownvarious binder resins can be added and used in addition to theabove-described resin to provide improved coating applicability to thebase material sheet and improved film-forming property or to adjust thecontent of polysiloxane segments. As the binder resin or resins to beused as described above, those chemically reactable with a crosslinkingagent such as the above-described polyisocyanate adduct or the like arepreferred, although even those having no reactivity can be also used inthe present invention.

As binder resins to be used as described above, it is possible to usethose employed conventionally for the formation of back-side,heat-resistant protective layers that make up thermal recording media,and no particular limitation is imposed. Usable examples include acrylicresins, polyurethane resins, polyester resins, polybutadiene resins,silicone resins, melamine resins, phenol resins, polyvinyl chlorideresins, cellulose resins, alkyd resins, modified cellulose resins,fluorinated resins, polyvinyl butyral resins, epoxy resins, polyamideresins, and the like. It is also possible to use resins obtained bymodifying the above-described resins with silicone or fluorine. When abinder resin is used in combination, it may be used or added in aproportion ranging preferably from 5 to 90 parts by mass, morepreferably from 10 to 60 parts by mass or so per 100 parts by mass ofthe polysiloxane-modified polyhydroxy polyurethane resin.

No particular limitation is imposed on the forming method of theheat-resistant protective layer that makes up the thermal recordingmedium according to the present invention. The heat-resistant protectivelayer can be formed, for example, by dissolving or dispersing theabove-mentioned polysiloxane-modified polyhydroxy polyurethane resin inan appropriate organic solvent, applying the resulting coatingformulation by a coating method such as the wire bar method, gravureprinting method or screen printing method or by a reverse roll coatingmethod making use of a gravure roll, and drying the resultant coatinglayer. The drying temperature in the above-described formation maypreferably be in a range of from 50 to 100° C. The thickness of theheat-resistant protective layer may be preferably from 0.001 to 2.00 μm,more preferably from 0.05 to 0.7 μm.

As the base material sheet for use in the thermal recording mediumaccording to the present invention, it is possible to use a film of apolycarbonate, polyarylate, polyether-imide, polysulfone, polyphenylether, polyamide-imide, polyimide, polyethylene naphthalate, polyphenylsulfide, polyether-ketone, fluorinated resin, or the like, or a film ofpolyethylene terephthalate (PET), polybutyleneterephthalate (PBT),polybutylene naphthalate (PBN), polyethylene, polypropylene,polystyrene, polyvinyl chloride, polyvinylidene chloride, a polyamide orthe like. A film having biaxial orientation is preferred. From theviewpoint of sensitivity in thermal recording, the thickness of the basematerial may be in a range that can be specified to be preferably 6 μmand smaller, more preferably from 2.5 μm to 4.5 μm.

As the ink layer in the thermal recording medium according to thepresent invention, any desired one of conventionally-known ink layerscan be used as it is, and no particular limitation is imposed. Describedspecifically, the ink layer for use in the present invention is formedfrom a colorant, a wax, a resin, and additives such as a lubricant andsurfactant. Usable examples of the colorant include pigments and dyes,such as carbon black, red iron oxide, Lake Red C, benzidine yellow,phthalocyanine green, phthalocyanine blue, direct dyes, oil dyes, andbasic dyes. The present invention is, however, not limited to theseexemplified compounds. Therefore, not only the above-mentionedillustrative compounds but also the compounds currently used in thermalfusion transfer recording methods or thermal sublimation transferrecording methods and readily available from the market are all usablein the present invention.

As the thermal recording medium according to the present invention usesthe above-described polysiloxane-modified polyhydroxy polyurethane resinof the present invention in the resin composition with which theheat-resistant protective layer arranged on the back side of the basematerial sheet is formed, the polysiloxane segments in the resin orientin the surface of the protective layer. The heat-resistant protectivelayer so formed is provided with heat resistance, lubricity andnon-tackiness to a thermal head, all of which the polysiloxane segmentsare equipped with. In addition, the hydroxyl groups in the structure ofthe polysiloxane-modified polyhydroxy polyurethane resin that forms theheat-resistant protective layer strongly interact with the base materialsheet at the interface between them, so that the heat-resistantprotective layer is provided with excellent adhesiveness to the basematerial, superb flexibility and outstanding antistatic effect.Therefore, the thermal recording medium can be provided with stillbetter performance. Further, the 5-membered cyclic carbonatepolysiloxane compound that makes up the resin for use in the presentinvention can incorporate carbon dioxide in the resin owing to the useof carbon dioxide as a production raw material. The present inventioncan, therefore, provide the thermal recording medium as anenvironment-responsive product, which is also useful from the viewpointof a reduction in carbon dioxide considered to be a cause of globalwarming and which is unavailable from conventional products.

<Imitation Leather>

The imitation leather according to the present invention ischaracterized in that the resin composition, which contains as aprincipal component the polysiloxane-modified polyhydroxy polyurethaneresin of the present invention derived from the reaction between the5-membered cyclic carbonate polysiloxane compound represented by theformula (1) and the amine compound, is filled in or laminated on thebase fabric.

Upon obtaining the imitation leather according to the present invention,the above-described resin composition which contains as a principalcomponent the polysiloxane-modified polyhydroxy polyurethane resin ofthe present invention is filled in or laminated on the base fabric. Thefilm made of the resin may be used as it is. Using a crosslinking agent,the film can also be formed into a crosslinked film. As the crosslinkingagent usable as described above, any crosslinking agent can be usedinsofar as it reacts with the hydroxyl groups in the resin structure.Examples include alkyl titanate compounds, polyisocyanate compounds, andthe like. No particular limitation is imposed on these polyisocyanatecompounds insofar as they are known and have been conventionally used inthe crosslinking of polyurethane resins. Illustrative are adducts or thelike of polyisocyanates, which have such structural formulas asdescribed above, with other compounds.

The resin composition, which is used for the formation of the imitationleather according to the present invention and contains as a principalcomponent the polysiloxane-modified polyhydroxy polyurethane resin ofthe present invention, can be used as a blend with one or more ofconventionally-known various resins to adjust the workability such asimpregnation, coating or covering applicability and the hand feeling andvarious performance of the imitation leather to be obtained. As otherresins to be used or blended, those chemically reactable with acrosslinking agent such as the above-described polyisocyanate adduct arepreferred, although even resins having no reactivity can be also used inthe present invention.

As resins usable in combination with the above-described resin,polyurethane-based resins which have been conventionally used as formingmaterials for imitation leathers are preferred although no particularlimitation is imposed. Usable examples include acrylic resins, polyesterresins, polybutadiene resins, silicone resins, melamine resins, phenolresins, phenoxy resins, vinyl chloride resin, vinyl chloride-vinylacetate resin, cellulose resins, alkyd resins, modified celluloseresins, fluorinated resins, polyvinyl butyral resins, epoxy resins,polyamide resins, and the like. It is also possible to use resinsobtained by modifying these resins with silicone or fluorine. When oneor more of these resins are used in combination, such a resin or resinsmay be used in a range of preferably from 5 to 90 parts by mass, morepreferably from 10 to 60 parts by mass or so per 100 parts by mass ofthe polysiloxane-modified polyhydroxy polyurethane resin.

To the resin composition which is used in the present invention andcontains as a principal component the polysiloxane-modified polyhydroxypolyurethane resin, one or more of various additives such asantioxidants, ultraviolet absorbers, anti-hydrolysis agents, pigments,dyes, flame retardants and fillers may be added in addition to one ormore of the above-described various additives.

The imitation leather according to the present invention ischaracterized in that the resin composition, which contains as aprincipal component the above-described polysiloxane-modifiedpolyhydroxy polyurethane resin, is filled in or laminated on the basefabric. No particular limitation is imposed on the production process ofthe imitation resin according to the present invention, and a knownproduction process of an artificial leather or synthetic leather can beused. In the imitation leather according to the present invention, thereis also included one produced by arranging a plasticizer-containing,vinyl chloride resin layer on a base fabric sheet and forming thereon aresin layer composed as a principal component of thepolysiloxane-modified polyhydroxy polyurethane resin which characterizesthe present invention.

As the base fabric (base material sheet) in the imitation leatheraccording to the present invention, base fabrics (base material sheets)which have been conventionally used in the production of imitationleathers are all usable, and no particular limitation is imposed.

Owing to the use of the specific polysiloxane-modified polyhydroxypolyurethane resin as a principal component in the imitation leatheraccording to the present invention as described above, the imitationleather can be provided with excellent pliability, lubricity, scratchresistance, abrasion resistance and chemical resistance. In addition,the hydroxyl groups which the polysiloxane-modified polyhydroxypolyurethane resin has strongly interact with the base fabric (basematerial sheet) at the interface between them. It is, therefore,possible to obtain the excellent performance that excellent adhesivenessto the base fabric, superb flexibility and outstanding antistatic effectare imparted, thereby making it possible to provide the imitationleather with improved performance. Further, the 5-membered cycliccarbonate polysiloxane compound that is employed in the synthesis of theresin for use in the present invention can incorporate carbon dioxide inthe resin owing to the use of carbon dioxide as a production rawmaterial. The present invention can, therefore, provide the imitationleather as an environment-responsive product, which is also useful fromthe viewpoint of a reduction in carbon dioxide considered to be a causeof global warming and which is unavailable from conventional products.

<Skin Material Made of Thermoplastic Polyolefin Resin>

The skin material according to the present invention, which is made ofthe thermoplastic polyolefin resin, has the top coat layer coated andformed directly on the thermoplastic polyolefin resin sheet, or theprimer layer coated on the resin layer and the top coat layer coated andformed on the primer layer. This skin material is characterized in thatas the high-molecular compound making up the top coat layer, theabove-described polysiloxane-modified polyhydroxy polyurethane resin,which has been derived from the reaction between the above-described5-membered cyclic carbonate polysiloxane compound represented by theformula (1) and the amine compound, is used.

Concerning the skin material according to the present invention, whichis made of the thermoplastic polyolefin resin, a matting agent may beadded with consideration to anti-glare properties depending on theapplication upon forming the top coat layer with thepolysiloxane-modified polyhydroxy polyurethane resin of the presentinvention. As the matting agent, a material composed of one fine powderor a combination of two or more fine powders selected from organic finepowders and inorganic fine powders can be used. No particular limitationis imposed on the organic fine powder or powders to be used as describedabove. Usable examples, however, include acrylic resin particles,styrene resin particles, styrene-acrylic resin particles, phenol resinparticles, melamine resin particles, acrylic-polyurethane resinparticles, polyurethane resin particles, polyester resin particles,nylon resin particles, silicone resin particles, polyethylene resinparticles, and the like. These powders may preferably have an averageparticle size in a range of from 0.1 to 10 μm. As their shapes, thosehaving a spherical shape or a substantially spherical shape arepreferred from a practical standpoint because the resulting coating filmcan be provided with particularly good matte properties.

On the other hand, the inorganic fine powders include talc, mica,calcium carbonate, barium sulfate, magnesium carbonate, clay, alumina,silica, carbon fibers, glass fibers, metal fibers, carbon black,titanium oxide, molybdenum, magnesium hydroxide, bentonite, graphite,and the like. As these powders, those composed of particles having anaverage particle size of 10 μm or smaller can conform to the object ofthe present invention, but the smaller the better.

Such a matting agent as described above may be used in a proportionranging from 1 to 150 parts by mass, preferably from 3 to 100 parts bymass per 100 parts by mass of the polysiloxane-modified polyhydroxypolyurethane resin. A proportion of smaller than 1 parts by mass cannotbring about sufficient matting effect, while a proportion of greaterthan 150 parts by mass may provide the resulting coating film withsignificantly lowered mechanical/physical properties. Proportionsoutside the above-described range are not preferred accordingly.

The polysiloxane-modified polyhydroxy polyurethane resin for use in thepresent invention is derived from the reaction between theabove-described 5-membered cyclic carbonate polysiloxane compoundrepresented by the formula (1) and the amine compound, and through thisreaction, hydroxyl groups are formed. The thus-formed hydroxyl groupsbring about further improvements in performance for the skin materialaccording to the present invention, which is made of the thermoplasticpolyolefin resin and has the top coat layer formed with theabove-described resin. Described specifically, these hydroxyl groupshave hydrophilicity. By the hydroxyl groups, the adhesiveness of the topcoat layer to the thermoplastic polyolefin resin sheet are henceimproved, and the antistatic effect unavailable from the conventionalproducts can also be obtained. Furthermore, the use of the reactionbetween the hydroxyl groups in the structure of the resin and acrosslinking agent or the like added to the resin can achieve furtherimprovements in the surface scratch resistance, abrasion resistance,chemical resistance and the like of the skin material product made ofthe thermoplastic polyolefin resin.

In the present invention, the top coat layer can be arranged by forminga film on the thermoplastic polyolefin resin with the composition, whichcontains as a principal component the polysiloxane-modified polyhydroxypolyurethane resin, or depending on the application, the compositioncontaining the matting agent (these compositions will hereinafter bereferred to simply as “the resin composition”) as it is. Further, acrosslinked film can be formed by incorporating a crosslinking agent inthe resin composition. As the crosslinking agent usable as describedabove, any crosslinking agent can be used insofar as it reacts with thehydroxyl groups in the resin structure. Examples include alkyl titanatecompounds, polyisocyanate compounds, and the like. No particularlimitation is imposed on the crosslinking agent insofar as it is a knowncrosslinking agent employed in the crosslinking of polyurethane resins.Illustrative are adducts or the like of polyisocyanates, which have suchstructural formulas as exemplified above, with other compounds.

The resin composition for use in the present invention may also containone or more other resins different from the polysiloxane-modifiedpolyhydroxy polyurethane resin in addition to this resin to improve itsspraying applicability or coating applicability to the thermoplasticpolyolefin resin and its film-forming property. As such other resins,conventionally-known various binder resins can be used or mixed. As thebinder resins, those chemically reactable with the crosslinking agentsuch as the above-described polyisocyanate adduct or the like arepreferred, although even those having no reactivity can be also used inthe present invention.

As these binder resins, various binder resins which have beenconventionally employed for skins of thermoplastic polyolefin resins canbe used, and no particular limitation is imposed. Usable examplesinclude acrylic resins, polyurethane resins, polyester resins,polybutadiene resins, silicone resins, melamine resins, phenol resins,polyvinyl chloride resins, cellulose resins, alkyd resins, modifiedcellulose resins, fluorinated resins, polyvinyl butyral resins, epoxyresins, polyamide resins, and the like. When a resin composition makingcombined use of such a binder resin is used, the binder resin may beused in a range of preferably from 5 to 90 parts by mass, morepreferably from 10 to 60 parts by mass or so per 100 parts by mass ofthe polysiloxane-modified polyhydroxy polyurethane resin thatcharacterizes the present invention.

In the resin composition for use in the present invention, one or moreof various additives for coating formulations, such as surface controlagents, fluidity control agents, ultraviolet absorbers, dispersants andanti-settling agents, may be further added as needed.

As the thermoplastic polyolefin resin sheet that makes up the skinmaterial according to the present invention, one made of one or more ofthe below-described materials can be used, for example. It is possibleto use, for example, a sheet made of at least one resin selected fromthe group consisting of low-density to high-density polyethylenes (LDPE,LLDPE, HDPE, etc.), polypropylenes such as polypropylene andpropylene-ethylene copolymer, and thermoplastic polyolefin resins suchas ethylene-propylene rubber (EPR), ethylene-butene rubber (EBR) andethylene-propylene-diene terpolymers (EPDM). Of these, a sheet made of apolypropylene resin or polyolefin-based thermoplastic elastomer ispreferred because it has good pliability and elasticity along withexcellent mechanical strength.

The thermoplastic polyolefin resin sheet is inert at the surfacethereof, and therefore, is inferior in the adhesiveness with a coatingto the surface. It is, therefore, preferred to directly apply theabove-mentioned resin composition to form a top coat layer afterphysically or chemically activating the surface by corona dischargetreatment or the like. It is also preferred to apply the above-mentionedresin composition to form a top coat layer via a primer layer afterforming the primer layer by applying a chlorinated polyolefin-basedresin or polyester-based resin and a polyisocyanate compound or apolyurethane resin and a polyisocyanate compound.

A film can be formed by applying the above-mentioned resin compositionon the thermoplastic polyolefin resin sheet directly or via the primerlayer in accordance with a known coating method such as brush coating,spray coating, roll coating, gravure coating or dip coating to give adry coat thickness of from 3 to 20 μm or so, and subsequent to drying,conducting heat treatment at a temperature of from 50 to 120° C. or so.The skin material according to the present invention, which has beenformed as a sheet as described above and is made of the thermoplasticpolyolefin resin, is formed into a desired shape, for example, by vacuummolding and is provided, for example, as a vehicle interior trimmaterial or an electric home appliance component or part.

In the skin material according to the present invention, which is madeof the thermoplastic polyolefin resin, the use of thepolysiloxane-modified polyhydroxy polyurethane resin of the presentinvention as a material for forming its top coat layer provides thesurface of the skin material with excellent lubricity, surface touchfeeling, scratch resistance, abrasion resistance, chemical resistance,and further, uniform matting effect. In addition, the hydroxyl groups inthe resin of the present invention employed for the formation of the topcoat layer strongly interact with the base material sheet at theinterface between them, thereby making it possible to obtain excellentperformance that the skin material is provided with excellentadhesiveness to the base material, superb flexibility and outstandingantistatic effect. Therefore, the skin material made of thethermoplastic polyolefin resin can be provided with improvedperformance. Further, the 5-membered cyclic carbonate polysiloxanecompound employed in the synthesis of the resin for use in the presentinvention can incorporate and fix carbon dioxide in the resin owing tothe use of carbon dioxide as a production raw material. The presentinvention can, therefore, provide the skin material made of thethermoplastic polyolefin resin as a product of an environment-responsivematerial, which is also useful from the viewpoint of a reduction incarbon dioxide considered to be a cause of global warming and which isunavailable from conventional products.

<Weather Strip Material>

The weather strip material according to the present invention is amaterial for coating and/or impregnating a high-molecular elastomermaterial to form a surface treatment layer at a slide contact portion tobe brought into sliding contact with another part, and is characterizedin that the weather strip material is a resin composition containing thepolysiloxane-modified polyhydroxy polyurethane resin of the presentinvention derived from the reaction between the above-described5-membered cyclic carbonate polysiloxane compound represented by theformula (1) and the amine compound.

The weather strip material according to the present invention is theabove-described resin composition containing the polysiloxane-modifiedpolyhydroxy polyurethane resin of the present invention, and the surfacetreatment layer is formed at the slide contact portion to be broughtinto sliding contact with another part by coating and/or impregnatingthe high-molecular elastomer material with the resin composition. As amore preferred embodiment of the resin composition, it is possible tomention a resin composition obtained by adding a diorganopolysiloxane,which has an average polymerization degree of from 5,000 to 100,000,and/or a silicone oil, which has a viscosity of from 100 to 1,000 cs, asan additive or additives in a proportion of from 1 to 100 parts by massper 100 parts by mass of the above-described polysiloxane-modifiedpolyhydroxy polyurethane resin of the present invention.

As the diorganopolysiloxane to be added to the above-described resin, itis preferred to use a linear, non-fluidity, rubbery silicone having anaverage polymerization degree of from 5,000 to 10,000. Such a materialis readily available from the market.

As the silicone oil to be added to the polysiloxane-modified polyhydroxypolyurethane resin of the present invention, one having a viscosity inthe range of from 100 to 1,000 cs is preferred. The silicone oil to beused as described above may have or may not have active hydrogen atomswhich can react with, for example, a polyisocyanate as a crosslinkingagent. It is to be noted that “cs” means “centistokes” as a unit ofkinematic viscosity. In general, each silicone oil is commercially soldwith this value as a specification criterion.

Such a diorganopolysiloxane and/or silicone oil as mentioned above maybe added in a proportion of from 1 to 100 parts by mass, preferably from3 to 70 parts by mass or so per 100 parts by mass of thepolysiloxane-modified polyhydroxy polyurethane resin. A proportion ofsmaller than 1 parts by mass cannot bring about sufficient effect by theaddition, while a proportion of greater than 100 parts by mass tends toprovide the resulting coating film with lowered mechanical/physicalproperties. Proportions outside the above-described range are notpreferred accordingly.

As another preferred embodiment of the resin composition, a mattingagent may be used as an additive to matt the surface of the resultingtreatment layer and to provide the surface of the resulting treatmentlayer with improved abrasion resistance and lubricity. Describedspecifically, it is preferred to obtain a resin composition by adding amaterial, which is composed of one fine powder or a combination of twoor more fine powders selected from organic fine powders and inorganicfine powders, as a matting agent in a proportion of from 1 to 150 partsby mass per 100 parts by mass of the resin for use in the presentinvention.

No particular limitation is imposed on the organic fine powder orpowders to be used as described above. Usable examples include acrylicresin particles, styrene resin particles, styrene-acrylic resinparticles, phenol resin particles, melamine resin particles,acrylic-polyurethane resin particles, polyurethane resin particles,polyester resin particles, nylon resin particles, silicone resinparticles, polyethylene resin particles, and the like. These powders maypreferably have an average particle size of from 0.1 to 10 μm or so. Astheir particle shapes, those having a spherical shape or a substantiallyspherical shape are preferred from a practical standpoint because theresulting coating film can be provided with particularly good matteproperties.

On the other hand, the inorganic fine powders include talc, mica,calcium carbonate, barium sulfate, magnesium carbonate, clay, alumina,silica, carbon fibers, glass fibers, metal fibers, carbon black,titanium oxide, molybdenum, magnesium hydroxide, bentonite, graphite,and the like. As the average particle size of particles that make upthese powders, 10 μm or smaller can conform to the object of the presentinvention, but powders having as smaller a particle size as possible aremore preferred.

Such a matting agent may be added in a proportion of from 1 to 150 partsby mass or so, preferably from 3 to 60 parts by mass per 100 parts bymass of the polysiloxane-modified polyhydroxy polyurethane resin. Aproportion of smaller than 1 parts by mass cannot bring about thematting effect sufficiently, while a proportion of greater than 150parts by mass tends to provide the resulting coating film withsignificantly lowered mechanical/physical properties. Proportionsoutside the above-described range are not preferred accordingly.

The polysiloxane-modified polyhydroxy polyurethane resin for use in thepresent invention is derived from the reaction between theabove-described 5-membered cyclic carbonate polysiloxane compoundrepresented by the formula (1) and the amine compound. When a surfacetreatment layer is formed by coating and/or impregnating thehigh-molecular elastomer material with the material of the presentinvention containing the resin, the hydroxyl groups formed by thereaction of the 5-membered cyclic carbonate groups in the structure ofthe resin with the amine compound can, therefore, provide the surface ofthe high-molecular elastomer with further improved performance.Described specifically, these hydroxyl groups have hydrophilicity andtherefore, can significantly improve the adhesiveness to thehigh-molecular elastomer material, and can also obtain antistatic effectwhich is unavailable from conventional products. Furthermore, theformation of the surface treatment layer by the use of the reactionbetween the hydroxyl groups in the resin and a crosslinking agent or thelike can achieve further improvements in surface heat resistance,abrasion resistance and chemical resistance of the surface.

In the present invention, the film (surface treatment layer) formed withthe resin composition, which contains the polysiloxane-modifiedpolyhydroxy polyurethane resin of the present invention, or thecomposition, which contains the resin and such various additives asmentioned above, (these compositions will hereinafter be referred tosimply as “the resin composition”) can bring about sufficient effects asit is. Further, a crosslinked film can be formed by using a crosslinkingagent. In this formation, any crosslinking agent can be used insofar asit reacts with the hydroxyl groups in the structure of the resin, and noparticular limitation is imposed. Examples include alkyl titanatecompounds and polyisocyanate compounds. Preferred are crosslinkingagents which are known and have been conventionally employed in thecrosslinking of polyurethane resins. Illustrative are adducts or thelike of polyisocyanates, which have such structural formulas asexemplified above, with other compounds.

In the resin composition containing the polysiloxane-modifiedpolyhydroxy polyurethane resin according to the present invention, anydesired one or more of conventionally-known various binder resins can beused or mixed to provide improved adhesiveness and film-forming propertywhen the resin composition is applied to a high-molecular elastomermaterial as a base material of a weather strip to form a surfacetreatment layer. As the binder resin or resins to be used as describedabove, those chemically reactable with a crosslinking agent such as theabove-described polyisocyanate adduct are preferred, although even thosehaving no reactivity can be also used in the present invention.

As these binder resins, binder resins which have been conventionallyemployed in the surface treatment of weather strips can be used, and noparticular limitation is imposed. Usable examples include acrylicresins, polyurethane resins, polyester resins, polybutadiene resins,silicone resins, melamine resins, phenol resins, polyvinyl chlorideresins, cellulose resins, alkyd resins, modified cellulose resins,fluorinated resins, polyvinyl butyral resins, epoxy resins, polyamideresins, and the like. When one or more of these binder resins are usedin combination, the binder resin or resins may be used or added in aproportion of preferably from 5 to 90 parts by mass, more preferablyfrom 10 to 60 parts by mass or so per 100 parts by mass of the resincomposition used in the present invention.

To the resin composition for use in the present invention, one or moreof various coating additives such as surface control agents, fluiditycontrol agents, ultraviolet absorbers, dispersants and anti-settlingagents may be added as needed.

By coating and/or impregnating the high-molecular elastomer as a weatherstrip base material with the resin composition, which contains thepolysiloxane-modified hydroxyl polyurethane resin of the presentinvention, in accordance with a known coating method such as brushcoating, spray coating, roll coating, gravure coating or dip coating, asurface treatment layer can be formed on the base material at a desiredposition thereof. Upon conducting the above-described formation, it ispreferred to form the film by applying the above-described resincomposition on the high-molecular elastomer to give a dry coat thicknessof from 10 to 100 μm or so, and subsequent to drying, conducting heattreatment at a temperature of from 50 to 150° C. or so.

By forming the surface treatment layer on the high-molecular elastomerat the desired position thereof with the resin composition that containsthe polysiloxane-modified polyhydroxy polyurethane resin of the presentinvention as described above, a weather strip excellent in lubricity,abrasion resistance, heat resistance and weatherability, and in apreferred embodiment, also in uniform matting effect can be obtained. Inaddition, the hydroxyl groups in the structure of thepolysiloxane-modified polyhydroxy polyurethane resin strongly interactwith the high-molecular elastomer as the base material at the interfacebetween them, so that the thus-formed surface treatment layer isprovided with excellent adhesiveness to the base material, superbflexibility and outstanding antistatic effect. Therefore, the weatherstrip obtained by forming its surface treatment layer with the materialof the present invention is provided with excellent performance.Further, the polysiloxane-modified polyhydroxy polyurethane resin foruse in the present invention can incorporate carbon dioxide in the resinbecause the specific 5-membered cyclic carbonate polysiloxane compoundused in the synthesis of the resin has been obtained by reacting anepoxy-modified polysiloxane compound and carbon dioxide. This means thatthe present invention makes it possible to provide a weather strip,which is responsive to the preservation of the environment, useful alsofrom the viewpoint of a reduction in greenhouse gas, and unavailablefrom conventional products.

EXAMPLES

The present invention will next be described in further detail based onspecific production examples, examples and comparative examples,although the present invention shall not be limited to these examples.It is to be noted that the terms “parts” and “%” in the followingexamples are on a mass basis unless otherwise specifically indicated.

Polysiloxane-Modified Polyhydroxy Polyurethane Resin Production Example1 Production of 5-Membered Cyclic Carbonate Polysiloxane Compound

To a reaction vessel equipped with a stirrer, thermometer, gas inlettube and reflux condenser, a divalent epoxy-modified polysiloxanerepresented the below-described formula (A) (100 parts),N-methylpyrrolidone (100 parts) and sodium iodide (1.2 parts) wereadded, followed by stirring into a homogeneous solution. Subsequently,the solution was stirred under heating at 80° C. for 30 hours whilebubbling carbon dioxide gas at a rate of 0.5 L/min. The divalentepoxy-modified polysiloxane used as described above was “X-22-163”(product of Shin-Etsu Chemical Co., Ltd.; epoxy equivalent: 198 g/mol),and its infrared spectrum is shown in FIG. 1.

(a: Value to give a molecular weight of 396)

After completion of the reaction, n-hexane (100 parts) was added to theresultant reaction mixture to dilute it. The diluted reaction mixturewas then washed three times with purified water (80 parts each time) ina separatory funnel to eliminate N-methylpyrrolidone and sodium iodide.The resulting n-hexane solution was then dried with magnesium sulfate,and was then concentrated to obtain, as a colorless clear liquid, a5-membered cyclic carbonate polysiloxane compound (1-A) (92 parts,yield: 89.7%).

In an infrared absorption spectrum (“FT-720”, manufactured by Horiba,Ltd.) of the thus-obtained reaction product (1-A), there was observed anabsorption around 1,800 cm⁻¹ as seen FIG. 2. This absorption isattributable to the carbonyl groups in the cyclic carbonate groups, andis not found on the raw material. The number average molecular weight ofthe reaction product was 2,450 (polystyrene equivalent; “GPC-8220”,manufactured by Tosoh Corporation) as shown in FIG. 3. In thethus-obtained 5-membered cyclic carbonate polysiloxane compound (1-A),carbon dioxide was fixed as much as 18.1%.

Production Example 2 Production of 5-Membered Cyclic CarbonatePolysiloxane Compound

In this production example, a divalent epoxy-modified polysiloxane Brepresented by the below-described formula (B) (“KF-105”, product ofShin-Etsu Chemical Co., Ltd.; epoxy equivalent: 485 g/mol) was used inplace of the divalent epoxy-modified polysiloxane (A) used above inProduction Example 1. By conducting a reaction as in Production Example1 except for the above-described change, a 5-membered cyclic carbonatepolysiloxane compound (1-B) (99 parts, yield: 91%) was obtained as acolorless clear liquid. The thus-obtained reaction product (1-B) wasidentified by infrared absorption spectroscopy, GPC and NMR as inProduction Example 1. In the thus-obtained 5-membered cyclic carbonatepolysiloxane compound (1-B), carbon dioxide was fixed as much as 8.3%.

(a: Value to give a molecular weight of 970)

Production Example 3 Production of 5-Membered Cyclic CarbonatePolysiloxane Compound)

In this production example, a divalent epoxy-modified polysiloxane Crepresented by the below-described formula (C) (“X-22-169AS”, product ofShin-Etsu Chemical Co., Ltd.; epoxy equivalent: 533 g/mol) was used inplace of the divalent epoxy-modified polysiloxane (A) used above inProduction Example 1. By conducting a reaction as in Production Example1 except the above-described change, a 5-membered cyclic carbonatepolysiloxane compound (1-C) (71 parts, yield: 68%) was obtained as acolorless clear liquid. The thus-obtained reaction product wasidentified by infrared absorption spectroscopy, GPC and NMR as inProduction Example 1. In the thus-obtained 5-membered cyclic carbonatepolysiloxane compound (1-C), carbon dioxide was fixed as much as 7.6%.

(a: Value to give a molecular weight of 1,066)

Comparative Production Example 1 Production of 5-Membered CyclicCarbonate Compound

In this comparative production example, a divalent epoxy compound Drepresented by the below-described formula (D) (“EPICOAT 828”, productof Japan Epoxy Resin Co., Ltd.; epoxy equivalent: 187 g/mol) was used inplace of the divalent epoxy-modified polysiloxane (A) used above inProduction Example 1. By conducting a reaction as in Production Example1 except for the above-described change, a 5-membered cyclic carbonatecompound (1-D) (118 parts, yield: 95%) was obtained as a white powder.

The reaction product was identified by infrared absorption spectroscopy,GPC and NMR. In the thus-obtained 5-membered cyclic carbonate compound(1-D), carbon dioxide was fixed as much as 19%.

Examples 1 to 3 Production of Polysiloxane-Modified PolyhydroxyPolyurethane Resins

Reaction vessels which were each equipped with a stirrer, thermometer,gas inlet tube and reflux condenser were purged with nitrogen. To thereaction vessels, the 5-membered cyclic carbonate polysiloxane compoundsobtained above in Production Examples 1 to 3 were added respectively. Toeach reaction vessel, N-methylpyrrolidone was added further to adjust asolids content to 35%, followed by stirring into a homogeneous solution.The corresponding amine compound described in Table 1 was then added inthe predetermined equivalent amount. The resulting mixture was stirredat a temperature of 90° C. for 10 hours so that a reaction was conducteduntil the amine compound was no longer detected.

The three kinds of polysiloxane-modified polyhydroxy polyurethane resinsof Examples 1 to 3 obtained as described above had properties as shownin Table 1.

Comparative Example 1 Production of Polyhydroxy Polyurethane Resin

A reaction vessel equipped with a stirrer, thermometer, gas inlet tubeand reflux condenser was purged with nitrogen. To the reaction vessel,the 5-membered cyclic carbonate compound obtained above in ComparativeProduction Example 1 was added. To the reaction vessel,N-methylpyrrolidone was added further to adjust a solids content to 35%,followed by stirring into a homogeneous solution. Hexamethylenediaminewas then added in a predetermined equivalent amount. The resultingmixture was stirred at a temperature of 90° C. for 10 hours so that areaction was conducted until the amine compound was no longer detected.The thus-obtained polyhydroxy polyurethane resin, which was free ofpolysiloxane segments, had properties as shown in Table 1.

TABLE 1 Compositions and Physical Properties of Polyhydroxy PolyurethaneResins Exam- Exam- Exam- Comp. ple 1 ple 2 ple 3 Ex. 1 Carbonatecompound (i) 1-A 1-B 1-C 1-D Amine compound (ii) HMDA¹⁾ BAPP²⁾ XDA³⁾HMDA¹⁾ Molar ratio (i/ii) 1.0 1.0 1.0 1.0 Solution viscosity 1.5 1.8 1.11.3 (35% conc., MPa · s) Number average 38,000 43,000 31,000 35,000molecular weight Hydroxyl number 175 83 76 215 (mgKOH/g) Polysiloxane 3257 62 0 content (%) Breaking strength 32.1 23.8 35.2 21.1 (20° C., MPa)Breaking extension 15 83 50 15 (20° C., %) Surface resistance 5.6 × 10¹²2.8 × 10¹³ 8.2 × 10¹³ 7.6 × 10¹⁰ (20° C. × 46% RH, Ω) Fixed amount ofcarbon 14.5 6.9 6.8 15.2 dioxide (%)⁴⁾ ¹⁾Hexamethylenediamine²⁾Bis-aminopropylpiperazine ³⁾Xylylenediamine ⁴⁾Calculated value

Comparative Example 2 Production of Polyester Urethane Resin

A conventional polyurethane resin of Comparative Example 2 wassynthesized from a polyester, diol and diamine as will be describedbelow. A reaction vessel equipped with a stirrer, thermometer, gas inlettube and reflux condenser was purged with nitrogen. In the reactionvessel, polybutylene adipate (average molecular weight: approx. 2,000;150 parts) and 1,4-butanediol (15 parts) were dissolved in a mixedorganic solvent consisting of methyl ethyl ketone (200 parts) anddimethylformamide (50 parts). Subsequently, under thorough stirring at60° C., a solution of hydrogenated MDI (62 parts) in dimethylformamide(171 parts) was gradually added dropwise, and after completion of thedropwise addition, a reaction was conducted at 80° C. for 6 hours.

The reaction mixture had a viscosity of 3.2 MPa·s (25° C.) at a solidscontent of 35%. A film obtained from the reaction mixture had a breakingstrength of 45 MPa, a breaking extension of 480%, and a thermalsoftening temperature of 110° C.

Comparative Example 3 Production of Polysiloxane-Modified PolyurethaneResin

A conventional, polysiloxane-modified polyurethane resin of ComparativeExample 3 was synthesized from a diol and diamine as will be describedbelow. Described specifically, a polydimethylsiloxane diol representedby the below-described formula (E) (average molecular weight: approx.3,200; 150 parts) and 1,4-butanediol (10 parts) were added to a mixedorganic solvent consisting of methyl ethyl ketone (200 parts) anddimethylformamide (50 parts), and a solution of hydrogenated MDI (40parts) in dimethylformamide (120 parts) was gradually added dropwise.After completion of the dropwise addition, a reaction was conducted at80° C. for 6 hours. The reaction mixture had a viscosity of 1.6 MPa·s(25° C.) at a solids content of 35%. A film obtained from the reactionmixture had a breaking strength of 21 MPa, a breaking extension of 250%,and a thermal softening temperature of 135° C.

(a: Value to give a molecular weight of 3,200)

Thermal Recording Media Examples 4 to 9 & Comparative Examples 4 to 9Formation of Heat-Resistant Protective Layers

Separately using the respective polyurethane resin solutions (solidscontent: 35%) prepared above in Examples 1 to 3 and Comparative Example1 to 3, heat-resistant protective layers were formed on surfaces of basematerial sheets, respectively. Described specifically, theabove-described resin solutions were diluted with a solvent to give adry coat thickness of 0.2 μm, to which a crosslinking agent was added asneeded to obtain coating formulations (resin compositions) the basiccompositions of which are shown in Table 2. The formulations wereapplied onto surfaces of polyethylene terephthalate films (products ofToray Industries, Inc., thickness: 3.5 μm) by gravure printing, and weredried in a drier to form heat-resistant protective layers on thesurfaces of the base material sheets, respectively. Further, thermalrecording layers (transfer ink layers) were formed on back sides of thebase material films (sheets), said back sides being the sides oppositeto the thus-formed heat-resistant protective layers, whereby thermalrecording media of Examples 4 to 9 and Comparative Examples 4 to 9 wereproduced, respectively. The formation of the transfer ink layers will bedescribed subsequently herein.

TABLE 2 Basic Compositions of Respective Coating Formulations (parts)Example 4 Resin of Ex. 1/crosslinking agent⁵⁾ = 100/0 Example 5 Resin ofEx. 1/crosslinking agent = 100/5 Example 6 Resin of Ex. 2/crosslinkingagent = 100/0 Example 7 Resin of Ex. 2/crosslinking agent = 100/5Example 8 Resin of Ex. 3/crosslinking agent = 100/0 Example 9 Resin ofEx. 3/crosslinking agent = 100/5 Comp. Ex. 4 Resin of Comp. Ex.1/crosslinking agent = 100/0 Comp. Ex. 5 Resin of Comp. Ex.1/crosslinking agent = 100/5 Comp. Ex. 6 Resin of Comp. Ex.2/crosslinking agent = 100/0 Comp. Ex. 7 Resin of Comp. Ex.2/crosslinking agent = 100/5 Comp. Ex. 8 Resin of Comp. Ex.3/crosslinking agent = 100/0 Comp. Ex. 9 Resin of Comp. Ex.3/crosslinking agent = 100/5 ⁵⁾Polyisocyanate (“COLONATE L”, product ofNippon Polyurethane Industry Co., Ltd.)

Comparative Example 10

A silicone resin (“KS-841”, product of Shin-Etsu Chemical Co., Ltd.; 100parts) and a catalyst (“PL-7”, product of Shin-Etsu Chemical Co., Ltd.;1 parts) were dissolved in toluene (1,000 parts) to prepare asilicone-based coating formulation of this comparative example. In asimilar manner as described above, the coating formulation was thenapplied onto a base sheet to form a heat-resistant protective layer.Further, a thermal recording layer (transfer ink layer) was formed on aback side of the base material film (sheet), said back side being theside opposite to the heat-resistant protective layer, whereby a thermalrecording medium was produced.

(Formation of Transfer Ink Layers)

On the back sides of the polyethylene terephthalate films, said backsides being opposite to the sides having the heat-resistant protectivelayers obtained as described above, transfer ink layers were formed toobtain the respective thermal recording media of Examples 4 to 9 andComparative Examples 4 to 10. Described specifically, an ink formulationof the below-described composition was heated to 100° C., and by a rollcoating method making use of the resultant hot melt, was applied ontothe back sides of the polyethylene terephthalate films, said back sidesbeing opposite to the sides having the heat-resistant protective layers,to give a wet coat thickness of 5 μm, whereby transfer ink layers wereformed. In the manner as described above, the thermal recording media ofExamples 4 to 9 and Comparative Examples 4 to 10, which used the resinsof the corresponding Examples and Comparative Examples, were obtained,respectively.

(Ink Formulation)

Paraffin wax 10 parts Carnauba wax 10 parts Polybutene  1 parts (productof Nippon Oil Corp.) Carbon black  2 parts

Evaluation

Using the respective film-shaped thermal recording media obtained asdescribed above, an on-machine thermal recording test was performed byprinting them under the below-described printing conditions. The“heat-resistant protective layer” formed on the back side of eachthermal recording medium was then evaluated by ranking its stickingtendency, thermal head smearing tendency, adhesiveness to the basematerial, coefficient of static friction, electrostatic chargingproperties, and environmental responsiveness. The ranking results arecollectively shown in Table 3.

(Printing Conditions for on-Machine Test of Thermal Recording Media)

-   Printer: “100XI III PLUS” (manufactured by Zebra Technologies    Corporation)-   Thermal head: “KPA-106-12TA(FLAT)” (manufactured by Kyocera    Corporation)-   Printing energy: 25 mJ/mm²-   Printing speed: 100 mm/sec-   Platen pressure: 350 gf/cm-   Receiving paper: Cast-coated paper (product of Lintec Corporation)-   Print pattern: CODE39 vertical bar code under printing conditions of    30 mm code width and approx. 40 mm length

(Sticking Tendency)

Sticking tendency was ranked by visually observing the separability ofthe “heat-resistant protective layer” of each thermal recording mediumfrom a thermal head upon pressing operation of the thermal recordingmedium against the thermal recording head when the thermal recordingmedium was subjected to the on-machine test. As ranking standards, thesticking tendency of the thermal recording medium was relatively rankedin 5 stages, one having best separability receiving “5”, while onehaving worst separability receiving “1”.

(Thermal Head Smearing Tendency)

The smearing of the thermal head was ranked by visually observing thestate of smear of the thermal head after each thermal recording mediumwas subjected to an on-machine thermal recording test. As rankingstandards, the thermal head smearing tendency of the thermal recordingmedium was relatively ranked in 5 stages, one causing least smearreceiving “5”, while one causing severest smear receiving “1”.

(Adhesiveness)

As an adhesiveness test, a 10×10 cross-cut cellophane tape peeling testwas conducted on the heat-resistant protective layer of each thermalrecording medium. The adhesiveness of the thermal recording medium wasranked based on the number of squares remaining after peeling.

(Coefficient of Static Friction)

With respect to the heat-resistant protective layer of each thermalrecording medium, its coefficient of static friction was measured byusing a surface property tester (manufacture by Shinto Scientific Co.,Ltd.).

(Blocking Tendency, Environmental Responsiveness)

By abruptly unrolling each film(sheet)-shaped thermal recording mediumfrom the state of a roll, the blocking tendency between rolled layers ofthe film by generated static electricity was visually observed. Theblocking tendency of the thermal recording medium was ranked “B” whenblocking occurred or “A” when no blocking occurred. The environmentalresponsiveness was ranked “A” or “B” depending on whether or not carbondioxide was fixed in the resin with which each “heat-resistantprotective layer” was formed.

TABLE 3 Ranking Results of Thermal Recording Media Head ElectrostaticSticking smearing Adhesive- Coefficient charging Environmental tendencytendency ness of friction properties responsiveness Example 4 5 5100/100 0.123 A A Example 5 5 5 100/100 0.105 A A Example 6 5 5 100/1000.115 A A Example 7 5 5 100/100 0.101 A A Example 8 5 5 100/100 0.120 AA Example 9 5 5 100/100 0.100 A A Comp. Ex. 4 1 (not traveled) — 100/1000.512 A A Comp. Ex. 5 1 (not traveled) — 100/100 0.410 A A Comp. Ex. 6 1(not traveled) —  0/100 0.612 B B Comp. Ex. 7 1 (not traveled) —  0/1000.522 B B Comp. Ex. 8 5 5 100/100 0.133 B B Comp. Ex. 9 5 5 100/1000.110 B B  Comp. Ex. 10 5 1 100/100 0.122 B B

Imitation Leathers Examples 10 to 15 & Comparative Examples 11 to 16Polymerization Examples 1-1, 2-1, 3-1 Polysiloxane-Modified PolyhydroxyPolyurethane Resins

Separately using the 5-membered cyclic carbonate polysiloxane compoundsobtained above in Production Examples 1 to 3, polysiloxane-modifiedpolyhydroxy polyurethane resins for use in the examples were synthesizedby such a procedure as will be described below. A reaction vesselequipped with a stirrer, thermometer, gas inlet tube and refluxcondenser was purged with nitrogen. To the reaction vessel, the5-membered cyclic carbonate polysiloxane compound obtained in eachProduction Example 1, 2 or 3 was added. To the reaction vessel,dimethylformamide was added further to adjust a solids content to 35%,followed by stirring into a homogeneous solution. The correspondingamine compound described in Table 4 was then added in a predeterminedamount. The resulting mixture was stirred at a temperature of 90° C. for10 hours so that a reaction was conducted until the amine compound wasno longer detected. The three kinds of polysiloxane-modified polyhydroxypolyurethane resins obtained as described above will be designated as“Polymerization Example 1-1”, “Polymerization Example 2-1” and“Polymerization Example 3-1”, and their properties were as shown inTable 4.

Comparative Polymerization Example 1-1 Production of PolyhydroxyPolyurethane Resin

A polyhydroxy polyurethane resin for use in the comparative example wassynthesized as will be described below. A reaction vessel equipped witha stirrer, thermometer, gas inlet tube and reflux condenser was purgedwith nitrogen. To the reaction vessel, the 5-membered cyclic carbonatecompound obtained in Comparative Production Example 1 was added. To thereaction vessel, dimethylformamide was added further to adjust a solidscontent to 35%, followed by stirring into a homogeneous solution.Hexamethylenediamine was then added in a predetermined amount. Theresulting mixture was stirred at a temperature of 90° C. for 10 hours sothat a reaction was conducted until the amine compound was no longerdetected. The resultant polyhydroxy polyurethane resin had properties asshown in Table 4.

TABLE 4 Compositions and Physical Properties of Polyhydroxy PolyurethaneResins Comp. Polymeri- Polymeri- Polymeri- Polymeri- zation zationzation zation Example Example Example Example 1-1 2-1 3-1 1-1 Carbonatecompound (i) 1-A 1-B 1-C 1-D Amine compound (ii) HMDA¹⁾ BAPP²⁾ XDA³⁾HMDA¹⁾ Molar ratio (i/ii) 1.0 1.0 1.0 1.0 Solution viscosity 1.5 1.8 1.11.3 (35% conc., MPa · s) Number average 38,000 43,000 31,000 35,000molecular weight Hydroxyl number 175 83 76 215 (mgKOH/g) Polysiloxanecontent (%) 32 57 62 0 Breaking strength 32.1 23.8 35.2 21.1 (20° C.,MPa) Breaking extension 15 83 50 15 (20° C., %) Surface resistance 5.6 ×10¹² 2.8 × 10¹³ 8.2 × 10¹³ 7.6 × 10¹⁰ (20° C. × 46% RH, Ω) Fixed amountof 14.5 6.9 6.8 15.2 carbon dioxide (%)⁴⁾ ¹⁾Hexamethylenediamine²⁾Bis-aminopropylpiperazine ³⁾Xylylenediamine ⁴⁾Calculated value

Comparative Polymerization Example 2-1 Production of Polyester UrethaneResin

A conventional polyurethane resin was synthesized as ComparativePolymerization Example 2-1 from a polyester, diol and diamine as will bedescribed below. A reaction vessel equipped with a stirrer, thermometer,gas inlet tube and reflux condenser was purged with nitrogen. In thereaction vessel, polybutylene adipate having an average molecular weightof approx. 2,000 (150 parts) and 1,4-butanediol (15 parts) weredissolved in a solvent consisting of dimethylformamide (250 parts).Subsequently, a solution of hydrogenated MDI (62 parts) indimethylformamide (171 parts) was gradually added dropwise at 60° C.under thorough stirring, and after completion of the dropwise addition,a reaction was conducted at 80° C. for 6 hours.

The reaction mixture had a viscosity of 3.2 MPa·s (25° C.) at a solidscontent of 35%. A film obtained from the reaction mixture had a breakingstrength of 45 MPa, a breaking extension of 480%, and a thermalsoftening temperature of 110° C.

Comparative Polymerization Example 3-1 Production ofPolysiloxane-Modified Polyurethane Resin

A polysiloxane-modified polyurethane resin for use in this comparativeexample was synthesized from the below-described diol and diamine aswill be described below. A polydimethyl siloxane diol represented by thebelow-described formula (E) and having an average molecular weight ofapprox. 3,200 (150 parts) and 1,4-butanediol (10 parts) were added todimethylformamide solvent (250 parts). Further, a solution ofhydrogenated MDI (40 parts) in dimethylformamide (120 parts) wasgradually added dropwise, and after completion of the dropwise addition,a reaction was conducted at 80° C. for 6 hours. The reaction mixture hada viscosity of 1.6 MPa·s (25° C.) at a solids content of 35%. A filmobtained from the reaction mixture had a breaking strength of 21 MPa, abreaking extension of 250%, and a thermal softening temperature of 135°C.

(a: Value to give a molecular weight of 3,200)

(Production of Imitation Leathers)

Separately using the reaction mixtures (solids content: 35%) ofPolymerization Examples 1-1, 2-1 and 3-1 and Comparative PolymerizationExamples 1-1, 2-1 and 3-1, coating formulations for imitation leatherswere prepared in accordance with the corresponding compositionsdescribed in Tables 5 and 6. Artificial leathers and synthetic leatherswere produced with the coating formulations, respectively, and wereranked by methods to be described subsequently herein.

Examples 10 to 12 & Comparative Examples 11 to 13 (Artificial Leathers)

Using coating formulations for imitation leathers, said coatingformulations containing the resins of Polymerization Examples 1-1, 2-1and 3-1 and Comparative Polymerization Examples 1-1, 2-1 and 3-1,respectively, nonwoven fabrics made of polystyrene-polyester fibers werecoated to give a thickness of 1 mm. The thus-coated non-woven fabricswere immersed in a 10% aqueous solution of DMF controlled at 25° C., sothat the resins were solidified. After washing, drying was conductedunder heat to obtain artificial leathers having porous layers as sheets.

Examples 13 to 15 & Comparative Examples 14 to 16 (Synthetic Leathers)

A base fabric sheet for imitation leathers was prepared by coating anddrying a solution of a polyurethane-based resin (“LETHAMINE UD-6025”,trade name, product of Dainichiseika Color & Chemicals Mfg., Co., Ltd.)as an adhesive layer on a woven fabric to give a dry coat thickness of10 μm. On the other hand, the coating formulations, which contained theresins obtained in Polymerization Examples 1-1, 2-1 and 3-1 andComparative Polymerization Examples 1-1, 2-1 and 3-1, were separatelycoated and dried on sheets of release paper to form films of approx. 15μm thickness, respectively. The thus-obtained films were bonded to cutpieces of the base fabric sheet to obtain synthetic leathers,respectively.

Evaluation

The respective imitation leathers obtained as artificial leathers andsynthetic leathers as described above were used. They were ranked by thebelow-described methods and standards to evaluate the imitationleathers. The ranking results are collectively shown in Tables 5 and 6.

(Hand Feeling)

The hand feeling of each imitation leather was determined by a handtouch feeling, and was ranked in accordance with the followingstandards.

A: Soft

B: A little hard

C: Hard

(Coefficient of Friction)

The coefficient of friction of the surface of each artificial leatherobtained as described above was measured by using the surface propertytester (manufacture by Shinto Scientific Co., Ltd.).

(Chemical Resistance)

Onto the surface of each synthetic leather obtained as described above,toluene was dropped. For allowing the surface to always remain in a wetstate, the solvent was additionally dropped. One hour later, the solventwas wiped off. A portion of the synthetic leather, where the droppedsolvent had been wiped off, was visually observed, and the chemicalresistance of the synthetic leather was ranked in accordance with thefollowing standards.

-   -   A: No trace of dropping was observed at all on the coated        surface.    -   B: A slight trace of dropping was recognized, but it was not        noticeable.    -   C: A clear trace of dropping was recognized.

(Surface Abrasion Resistance)

Using a plane abrasion tester, each synthetic leather obtained asdescribed above was rubbed by reciprocating No. 6 canvas under a load of1 kgf. The number of reciprocations until occurrence of a scratch wascounted.

-   -   A: 5,000 reciprocations or more    -   B: 2,000 reciprocations or more, but less than 5,000        reciprocations    -   C: Less than 2,000 reciprocations

(Environmental Responsiveness)

The environmental responsiveness of each imitation leather was ranked“A” or “B” depending on whether or not carbon dioxide was fixed in theused resin.

TABLE 5 Compositions of Coating Formulations and Ranking Results(Artificial Leathers) (unit: parts) Examples Comparative Examples 10 1112 11 12 13 Resin of 100 — — — — — Polymerization Example 1-1 Resin of —100 — — — — Polymerization Example 2-1 Resin of — — 100 — — —Polymerization Example 3-1 Resin of — — — 100 — — ComparativePolymerization Example 1-1 Resin of — — — — 100 — ComparativePolymerization Example 2-1 Resin of — — — — — 100 ComparativePolymerization Example 3-1 Hand feeling A A A B A A Coefficient of 0.1530.174 0.162 0.378 0.507 0.155 friction Environmental A A A A B Bresponsiveness

TABLE 6 Compositions of Coating Formulations and Ranking Results(Synthetic Leathers) (unit: parts) Comparative Examples Examples 13 1415 14 15 16 Resin of 100 — — — — — Polymerization Example 1-1 Resin of —50 — — — — Polymerization Example 2-1 Resin of — — 50 — — —Polymerization Example 3-1 Resin of — — — 100 — — ComparativePolymerization Example 1-1 Resin of — 50 — — 100 — ComparativePolymerization Example 2-1 Resin of — — 50 — — 100 ComparativePolymerization Example 3-1 Crosslinking agent  3  3  3  3  3  3 Handfeeling A A A B A A Chemical resistance A A A A B B Surface abrasion A AA A C A resistance Environmental A A A A B B responsiveness Crosslinkingagent in the table: “COLONATE HX”, trade name, product of NipponPolyurethane Industry Co., Ltd.)

Separately using the polyurethane resins of Examples 1 to 3 andComparative Examples 1-3 prepared as described above, synthetic leathersand artificial leathers were produced in a similar manner as describedabove and were ranked likewise. Similar results as described above wereobtained.

Skin Materials Made of Thermoplastic Polyolefin Resins Examples 16 to 21& Comparative Examples 17 to 22 (Used Polyurethane Resins)

In Examples 16 to 21, the polysiloxane-modified polyhydroxy polyurethaneresins, which were obtained in Polymerization Examples 1-1, 2-1 and 3-1and were used for the production of imitation leathers as describedabove, were used. In Comparative Examples 17 and 18, the polyhydroxypolyurethane resin of Comparative Polymerization Example 1-1 used abovefor the production of imitation leathers was used. In ComparativeExamples 19 and 20, there was used a polyester urethane resin solutionproduced in a similar manner as in the production of the polyesterurethane resin of Comparative Polymerization Example 2-1, which wasconducted above upon production of imitation leathers, except that amixed organic solvent consisting of methyl ethyl ketone (200 parts) anddimethylformamide (50 parts) was used in place of the solvent consistingof dimethylformamide (250 parts). The solution had a viscosity of 3.2MPa·s (25° C.) at a solids content of 35%. A film obtained from thesolution had a breaking strength of 45 MPa, a breaking extension of480%, and a thermal softening temperature of 110° C. In ComparativeExamples 21 and 22, there was used a polysiloxane-modified polyurethaneresin solution produced in a similar manner as in the production of thepolysiloxane-modified polyurethane resin of Comparative PolymerizationExample 3-1, which was conducted above upon production of imitationleathers, except that a mixed organic solvent consisting of methyl ethylketone (200 parts) and dimethylformamide (50 parts) was used in place ofthe solvent consisting of dimethylformamide (250 parts). The solutionhad a viscosity of 1.6 MPa·s (25° C.) at a solids content of 35%. A filmobtained from the solution had a breaking strength of 21 MPa, a breakingextension of 250%, and a thermal softening temperature of 135° C.

(Production of Skin Materials Made of Thermoplastic Polyolefin Resins)

Separately using the above-described polyurethane resins, coatingformulations for skins, the principal compositions of which aredescribed in Tables 7 and 8, were prepared. With those coatingformulations, skin materials made of thermoplastic polyolefin resinswere produced as will be described below. The thus-obtained, respectiveskin materials were ranked by the following methods and standards.

A base material sheet of a thermoplastic polyolefin was subjected tocorona discharge treatment to activate its surface to a wetting index of45 dyn/cm. Onto the resulting base material sheet, chlorinatedpolypropylene (“SUPERCHLON”, product of Nippon Paper Chemicals Co.,Ltd.) was coated by a 120-mesh gravure roll to give a dry coat thicknessof 3 μm, followed by drying at 100° C. for 2 minutes to form a primerlayer. Onto cut pieces of the thus-formed coating film, the coatingformulations for skins as described in Tables 7 and 8 were applied,respectively, by a 120-mesh gravure roll to give a dry coat thickness of5 μm. The coating formulations so applied were dried at 100° C. for 2minutes, and then aged at 80° C. for 24 hours to obtain skin materials(sheets) provided with top coat layers, respectively. Those skinmaterials were then molded by a vacuum molding machine equipped with aconvex mold controlled at 160° C. at a surface thereof, whereby moldedproducts were obtained, respectively.

Evaluation

The molded products obtained as described above were ranked formoldability, gloss (luster), coefficient of friction, adhesiveness,scratch resistance, oil resistance, chemical resistance, surfaceabrasion resistance, and environmental responsiveness by thebelow-described methods and standards, and those molded products wereevaluated. Especially, the surfaces (top coat layers) of the moldedproducts formed of the respective sheets were evaluated. The results areshown in Table 7 and Table 8.

(Moldability)

The surface of each sheet after its vacuum molding was visually observedand ranked.

-   -   A: Good (No molding cracking or whitening phenomenon)    -   B: Bad (Either molding cracking or whitening phenomenon is        observed)

(Gloss Value)

Following JIS K5600, the luster of the surface of each sheet after itsvacuum molding was measured by a gloss meter. A gloss value of 1.2 orsmaller (standard value required in the relevant business field) was setto pass.

(Coefficient of Friction)

The coefficient of friction of the surface of each sheet after itsvacuum molding was measured by the surface property tester (manufactureby Shinto Scientific Co., Ltd.). A coefficient of friction of not higherthan 0.2 was set to be desired, because a lower coefficient of frictionleads to a smaller abnormal noise (squeak noise) by friction between thesurfaces of vehicle interior trim materials.

(Adhesiveness)

On the surface of each sheet after its vacuum molding, a cross-cutcellophane tape peeling test was conducted. The adhesiveness of thesheet was ranked in accordance with the following standards.

A: Good (No peeled portion in the coated surface)

B: Bad (Peeled area at the coated surface)

(Scratch Resistance)

The surface of each sheet after its vacuum molding was rubbed with anail. By visually observing whether or not a trace of scratch orwhitening had occurred, the scratch resistance of the sheet was rankedin accordance with the following standards.

-   -   A: Good (Nail scratch or whitening is hardly noticeable at the        coated surface)    -   B: Bad (Nail scratch or a trace of whitening is clearly        noticeable at the coated surface)

(Oil Resistance)

The surface of each sheet after its vacuum molding was coated over anarea of 2 cm in radius with beef tallow (Nacalai Tesque, Inc.), and thesheet so coated was left over for 5 days in an atmosphere of 80° C.Subsequently, the beef tallow was removed. On the area where the coatedbeef tallow had been removed, a cross-cut cellophane tape peeling testwas conducted to rank the oil resistance of the sheet.

(Chemical Resistance)

Onto the surface of each sheet after its vacuum molding, ethanol wasdropped. For allowing the surface to always remain in a wet state, thesolvent was additionally dropped. One hour later, the solvent was wipedoff. A portion of the sheet, where the dropped solvent had been wipedoff, was visually observed, and the chemical resistance of the sheet wasranked in accordance with the following standards.

-   -   A: No trace of dropping was observed at all on the coated        surface.    -   B: A slight trace of dropping was recognized, but it was not        noticeable.    -   C: A clear trace of dropping was recognized.

(Surface Abrasion Resistance)

Using a plane abrasion tester, the surface of each sheet after itsvacuum molding was rubbed by reciprocating No. 6 canvas under a load of1 kgf. The number of reciprocations until occurrence of a scratch wascounted. The surface abrasion resistance of the sheet was ranked inaccordance with the following standards.

-   -   A: 5,000 reciprocations or more    -   B: 2,000 reciprocations or more, but less than 5,000        reciprocations    -   C: Less than 2,000 reciprocations

(Environmental Responsiveness)

The environmental responsiveness of each skin material was ranked “A” or“B” depending on whether or not carbon dioxide was fixed in the resinused for the formation of the top coat layer of the skin material.

TABLE 7 Compositions of Coating Formulations for Skin Materials of theExamples and Ranking Results of Molded Products Examples 16 17 18 19 2021 Primer Chlorinated polypropylene Resin of Polymerization Example 1-1(parts) 100 100 — — — — Resin of Polymerization Example 2-1 (parts) — —100 100 — — Resin of Polymerization Example 3-1 (parts) — — — — 100 100Matting agents Resin particles^(a)) 35 25 35 25 35 25 (parts)Silica^(b)) — 10 — 10 — 10 Crosslinking agent^(c)) (parts) 3 3 3 3 3 3Moldability A A A A A A Gloss value 0.9 0.7 0.9 0.7 1.0 0.9 Coefficientof friction 0.135 0.125 0.165 0.147 0.176 0.154 Adhesiveness A A A A A AScratch resistance A A A A A A Oil resistance A A A A A A Chemicalresistance A A A A A A Surface abrasion resistance A A A A A AEnvironmental responsiveness A A A A A A ^(a))“FINE POLYURETHANEPARTICLES” (product of Dainichiseika Color & Chemicals Mfg., Co., Ltd.,5 μm on average) ^(b))“NIPSIL” (product of Nippon Silica Industry Co.,Ltd.) ^(c))“COLONATE HX” (product of Nippon Polyurethane Industry Co.,Ltd.)

TABLE 8 Compositions of Coating Formulations for Skin Materials of theComparative Examples and Ranking Results of Molded Products ComparativeExamples 17 18 19 20 21 22 Primer Chlorinated polypropylene Resin ofComp. Polymerization Ex. 1-1 (parts) 100 100 — — — — Resin of Comp.Polymerization Ex. 2-1 (parts) — — 100 100 — — Resin of Comp.Polymerization Ex. 3-1 (parts) — — — — 100 100 Matting agents Resinparticles^(a)) 35 25 35 25 35 25 (parts) Silica^(b)) — 10 — 10 — 10Crosslinking agent^(c)) (parts) 3 3 3 3 3 3 Moldability A A A A A AGloss value 0.9 0.7 1.5 1.3 1.0 0.9 Coefficient of friction 0.287 0.2450.420 0.382 0.141 0.128 Adhesiveness A A A B A A Scratch resistance A AB B A A Oil resistance A A B B B B Chemical resistance A A B B B BSurface abrasion resistance A A C C A A Environmental responsiveness A AB B B B ^(a))“FINE POLYURETHANE PARTICLES” (product of DainichiseikaColor & Chemicals Mfg., Co., Ltd., 5 μm on average) ^(b))“NIPSIL”(product of Nippon Silica Industry Co., Ltd.) ^(c))“COLONATE HX”(product of Nippon Polyurethane Industry Co., Ltd.)

Weather Strip Materials Examples 22 to 27 & Comparative Examples 23 to26 (Used Polyurethane Resins)

In Examples 22 to 27, the polysiloxane-modified polyhydroxy polyurethaneresins, which were obtained in Polymerization Examples 1-1, 2-1 and 3-1and were used above for the production of imitation leathers, were used.In Comparative Examples 23 and 24, a similar polyester urethane resinsolution as that used in Comparative Example 15 of the skin materialmade of the thermoplastic polyolefin resin was used. In ComparativeExamples 25 and 26, a similar polysiloxane-modified polyurethane resinsolution as that used in Comparative Example 16 of the skin materialmade of the thermoplastic polyolefin resin was used. Separately usingthe polyurethane resins, coating formulations (resin compositions) wereprepared in accordance with the corresponding compositions shown inTables 9 and 10 to provide them as the weather strip materials ofExamples 22 to 27 and Comparative Examples 23 to 26, respectively.Further, those coating formulations were applied by an air spray gunonto EPDM rubber sheets, followed by drying at 100° C. for 10 minutes toform films of 20 μm, respectively. The EPDM rubber sheets, which hadbeen obtained as described above and had the films, were provided asmeasurement samples for the ranking of the surface treatment layers(films) formed by the respective weather strip materials.

Evaluation

The weather strip materials and measurement samples prepared as descriedabove were measured for coefficient of static friction, coefficient ofkinetic friction, contact angle, adhesiveness, abrasion durability,weatherability and the like by the below-described methods, and thematerials of the examples and comparative examples were ranked. Rankingresults are collectively shown in Tables 9 and 10.

(Coefficient of Static Friction, Coefficient of Kinetic Friction)

The coefficient of static friction and coefficient of kinetic frictionof each weather strip material (film) against a glass member weremeasured by using the surface property tester (manufacture by ShintoScientific Co., Ltd.).

(Contact Angle)

The contact angle to water at the film portion of each measurementsample obtained as described above was measured by a contact angle meter(manufactured by Kyowa Interface Science Co., Ltd.), and was recorded asthe contact angle of the film, which was formed of the correspondingweather strip material, to water.

(Adhesiveness)

On the film portion of each measurement sample obtained as describedabove, a cross-cut cellophane tape peeling test was conducted. Theadhesiveness of the film formed of the corresponding weather stripmaterial was ranked in accordance with the following standards.

A: Good (No peeled portion in the film)

B: Bad (Peeled area on the film)

(Abrasion Durability)

A glass plate was brought under a load of 9.8 N into contact with thefilm portion of each measurement sample obtained as described above, andthe glass plate was reciprocated. The number of reciprocations untiloccurrence of a tear in the film was counted by the surface propertytester (manufacture by Shinto Scientific Co., Ltd.). Based the number ofthe reciprocations so counted, the abrasion durability of the filmformed of the corresponding weather strip material was ranked.

(Weatherability Test)

Using a “SUNSHINE CARBON ARC WEATHER METER” (Suga Test Instruments Co.,Ltd.), the film portion of each measurement sample obtained as describedabove was exposed to light at a panel temperature of 83° C. for 200hours. The conditions of the film surface were then visually observed,and the weatherability of the surface of the film formed of thecorresponding weather strip material was ranked in accordance with thefollowing standards.

3: No changes in surface conditions

2: Some changes in surface conditions

1: Significant changes and whitening phenomenon

(Environmental Responsiveness)

The environmental responsiveness of each weather strip material wasranked “A” or “B” depending on whether or not carbon dioxide was fixedin the weather strip material (film).

TABLE 9 Ranking Results of Examples Examples 22 23 24 25 26 27 Resin ofPolymerization Example 1-1 (parts) 100 100 — — — — Resin ofPolymerization Example 2-1 (parts) — — 100 100 — — Resin ofPolymerization Example 3-1 (parts) — — — — 100 100 Matting agents Resinparticles^(a)) — 25 — 25 — 25 (parts) Silica^(b)) 10 10 10 10 10 10Silicone oil^(c)) (parts) — 20 — 20 — 20 Crosslinking agents^(d))(parts) 3 3 3 3 3 3 Coefficient of static friction 0.33 0.28 0.38 0.300.35 0.27 Coefficient of kinetic friction 0.17 0.14 0.16 0.14 0.16 0.14Contact angle (°) 109 112 110 112 112 113 Adhesiveness A A A A A AAbrasion durability (×10⁴ reciprocations) 14 16 13 15 13 15Weatherability test 3 3 3 3 3 3 Environmental responsiveness A A A A A A^(a))“FINE POLYURETHANE PARTICLES” (product of Dainichiseika Color &Chemicals Mfg., Co., Ltd., 5 μm on average) ^(b))“NIPSIL” (product ofNippon Silica Industry Co., Ltd.) ^(c))“KF96H” (product of Shin-EtsuChemical Co., Ltd.) ^(d)) “COLONATE HX” (product of Nippon PolyurethaneIndustry Co., Ltd.)

TABLE 10 Ranking Results of Comparative Examples Comparative Examples 2324 25 26 Resin of Comparative 100 100 — — Polymerization Example 2-1(parts) Resin of Comparative — — 100 100 Polymerization Example 3-1(parts) Matting Resin — 25 — 25 agents particles^(a)) (parts)Silica^(b)) 10 10 10 10 Silicone oil^(c)) (parts) — 20 — 20 Crosslinkingagent^(d)) (parts) 3 3 3 3 Coefficient of static friction 0.65 0.58 0.350.27 Coefficient of kinetic friction 0.25 0.16 0.17 0.15 Contact angle(°) 86 110 112 113 Adhesiveness B B B B Abrasion durability (×10⁴ 4 9 810 reciprocations) Weatherability test 1 1 2 2 Environmentalresponsiveness B B B B ^(a))“FINE POLYURETHANE PARTICLES” (product ofDainichiseika Color & Chemicals Mfg., Co., Ltd., average particle size:5 μm) ^(b))“NIPSIL” (product of Nippon Silica Industry Co., Ltd.)^(c))“KF96H” (product of Shin-Etsu Chemical Co., Ltd.) ^(d))“COLONATEHX” (product of Nippon Polyurethane Industry Co., Ltd.)

INDUSTRIAL APPLICABILITY

According to the present invention, there is provided a novelpolysiloxane-modified polyhydroxy polyurethane resin, which is excellentin lubricity, abrasion resistance, chemical resistance, non-tackiness,antistatic properties, heat resistance and the like, can replaceconventional fossil-based plastics, and is useful as film and moldingmaterials, various coating materials, various binders, and so on. Theresin provided by the present invention can use carbon dioxide as aproduction raw material, the present invention makes it possible toprovide products which are responsive to the global environment and cancontribute to a reduction in carbon dioxide as a greenhouse gas. Thepresent invention, therefore, is also expected to find a wide variety ofutility from this respect. This resin can be used, for example, in thebelow-described fields. The use of the resin according to the presentinvention makes it possible to obtain products, which are no wayinferior to those obtained by using conventional fossil-based materialsand are further added with new performance although they are productsresponsive to the global environment.

By forming a heat-resistant protective layer, which makes up a thermalrecording medium, with the above-described resin of the presentinvention, the polysiloxane segments in the resin orient in a surface,thereby making it possible to provide the heat-resistant protectivelayer with heat resistance, slidability and non-tackiness to a thermalhead, all of which the polysiloxane segments are equipped with. Inaddition, the hydroxyl groups which the polysiloxane-modifiedpolyhydroxy polyurethane resin has strongly interact with a basematerial sheet at the interface between them, so that the heat-resistantprotective layer is provided with excellent adhesiveness to the basematerial, superb flexibility, and outstanding antistatic effect. Thethermal recording medium can, therefore, be obtained with theheat-resistant protective layer that shows excellent performance.

Owing to the use of a resin composition, which contains the resin of thepresent invention as a principal component, in the production of animitation leather, the resulting imitation leather can be provided withexcellent pliability, lubricity, scratch resistance, abrasion resistanceand chemical resistance. In addition, the hydroxyl groups in thestructure of the polysiloxane-modified polyhydroxy polyurethane resinstrongly interact with a base fabric (base material sheet) at theinterface between them. It is, therefore, possible to obtain outstandingperformance that excellent adhesiveness to the base fabric, superbflexibility, and outstanding antistatic effect are imparted.

Owing to the use of a composition, which contains thepolysiloxane-modified polyhydroxy polyurethane resin of the presentinvention, in a top coat layer of a thermoplastic polyolefin resin sheetwhich makes up a skin material made of the thermoplastic polyolefinresin and is useful as a vehicle interior trim material or the like, thepolysiloxane segments in the resin orient in the surface so that amolded product obtained from the skin material is excellent inlubricity, surface touch feeling, scratch resistance, abrasionresistance and chemical resistance, and moreover, superb in uniformmatting effect. In addition, the hydroxyl groups contained in thepolysiloxane-modified polyhydroxy polyurethane resin, which forms thetop coat layer, strongly interact with a base material sheet at theinterface between them. It is, therefore, possible to obtain outstandingperformance that excellent adhesiveness and flexibility are exhibitedand antistatic effect is imparted.

By using as a weather strip material a resin composition that containsthe polysiloxane-modified polyhydroxy polyurethane resin of the presentinvention, a film can be obtained with excellent lubricity, abrasionresistance, heat resistance, weatherability and uniform matting effectwhen the material is coated on or impregnated in a high molecularelastomer material (base material sheet). In addition, the hydroxylgroups in the polysiloxane-modified polyhydroxy polyurethane resinstrongly interact with the base material sheet at the interface betweenthem, so that a film of outstanding performance can be obtained withsuperb adhesiveness, flexibility and antistatic effect imparted thereto.

1. A polysiloxane-modified polyhydroxy polyurethane resin characterizedby being derived from a reaction between a 5-membered cyclic carbonatepolysiloxane compound represented by the following formula (1) and anamine compound:

wherein A means

in which R₁ means an alkylene group which has from 1 to 12 carbon atomsand may have therein a linkage by an element of O, S or N and/or alinkage by —(C₂H₄O)_(b)—, R₂ means a direct bond or an alkylene grouphaving from 2 to 20 carbon atoms, R₂ may be linked to an alicyclic groupor aromatic group, b stands for a number of from 1 to 300, and a standsfor a number of from 1 to
 300. 2. The polysiloxane-modified polyhydroxypolyurethane resin according to claim 1, wherein the 5-membered cycliccarbonate polysiloxane compound has been obtained by reacting anepoxy-modified polysiloxane compound with carbon dioxide.
 3. Thepolysiloxane-modified polyhydroxy polyurethane resin according to claim2, which contains from 1 to 25 mass % of carbon dioxide derived from araw material.
 4. The polysiloxane-modified polyhydroxy polyurethaneresin according to claim 1, wherein a content of polysiloxane segmentsin a molecule of the resin is from 1 to 75 mass %.
 5. A process forproducing a polysiloxane-modified polyhydroxy polyurethane resin, whichcomprises deriving from a reaction between a 5-membered cyclic carbonatepolysiloxane compound represented by the following formula (1) and anamine compound:

wherein A means

in which R₁ means an alkylene group which has from 1 to 12 carbon atomsand may have therein a linkage by an element of O, S or N and/or alinkage by —(C₂H₄O)_(b)—, R₂ means a direct bond or an alkylene grouphaving from 2 to 20 carbon atoms, R₂ may be linked to an alicyclic groupor aromatic group, b stands for a number of from 1 to 300, and a standsfor a number of from 1 to
 300. 6. The process according to claim 5,wherein as the 5-membered cyclic carbonate polysiloxane compound, a5-membered cyclic carbonate polysiloxane compound obtained by reactingan epoxy-modified polysiloxane compound represented by the followingformula (2) with carbon dioxide is used:

wherein A means

in which R₁ means an alkylene group which has from 1 to 12 carbon atomsand may have therein a linkage by an element of O, S or N and/or alinkage by —(C₂H₄O)_(b)—, R₂ means a direct bond or an alkylene grouphaving from 2 to 20 carbon atoms, R₂ may be linked to an alicyclic groupor aromatic group, b stands for a number of from 1 to 300, and a standsfor a number of from 1 to
 300. 7. A polysiloxane-modified polyhydroxypolyurethane resin composition comprising the polysiloxane-modifiedpolyhydroxy polyurethane resin according to claim 1 and another resin.8. A polysiloxane-modified polyhydroxy polyurethane resin compositioncomprising the polysiloxane-modified polyhydroxy polyurethane resinaccording to claim 1 and a crosslinking agent reactable with hydroxylgroups existing in a structure of the polysiloxane-modified polyhydroxypolyurethane resin.
 9. A thermal recording medium having a base materialsheet, a thermal recording layer arranged on at least one side of thebase material sheet, and a heat-resistant protective layer arranged onanother side of the base material sheet, said another side being a backside to be brought into contact with a thermal head, wherein theheat-resistant protective layer is formed with a resin composition thatcomprises at least the polysiloxane-modified polyhydroxy polyurethaneresin according to claim
 1. 10. The thermal recording medium accordingto claim 9, wherein the resin composition further comprises anotherresin.
 11. The thermal recording medium according to claim 9, whereinthe heat-resistant protective layer is a film crosslinked by a reactionbetween hydroxyl groups, which exist in a structure of thepolysiloxane-modified polyhydroxy polyurethane resin, and a crosslinkingagent reactable with the hydroxyl groups.
 12. The thermal recordingmedium according to claim 9, wherein the base material sheet has athickness in a range which is specified to be from 2.5 μm to 4.5 μm. 13.The thermal recording medium according to claim 9, wherein theheat-resistant protective layer has a thickness in a range of from 0.001to 2.00 μm.
 14. An imitation leather comprising a base fabric and aresin composition comprising as a principal component thereof thepolysiloxane-modified polyhydroxy polyurethane resin according to claim1 and impregnated in or laminated on the base fabric.
 15. The imitationleather according to claim 14, wherein the resin composition furthercomprises another resin.
 16. The imitation leather according to claim14, wherein the polysiloxane-modified polyhydroxy polyurethane resin inthe resin composition impregnated in or laminated on the base fabric hasbeen crosslinked by a reaction between hydroxyl groups existing in astructure of the resin and a crosslinking agent reactable with thehydroxyl groups.
 17. A skin material made of a thermoplastic polyolefinresin, comprising a thermoplastic polyolefin resin sheet and a top coatlayer formed directly or via a primer layer on the sheet, wherein thetop coat layer comprises as a principal component thereof thepolysiloxane-modified polyhydroxy polyurethane resin according toclaim
 1. 18. The skin material according to claim 17, wherein the topcoat layer has been formed with a resin composition which comprises thepolysiloxane-modified polyhydroxy polyurethane resin and as a mattingagent, a material composed of one fine powder or a combination of two ormore fine powders selected from organic fine powders and inorganic finepowders and added in a proportion of from 1 to 150 parts by mass per 100parts by mass of the polysiloxane-modified polyhydroxy polyurethaneresin.
 19. The skin material according to claim 17, wherein the top coatlayer has been formed with a resin composition which comprises, inaddition to the polysiloxane-modified polyhydroxy polyurethane resin,another resin different from the polysiloxane-modified polyhydroxypolyurethane resin.
 20. The skin material according to claim 17, whereinthe top coat layer is a film crosslinked by a reaction between hydroxylgroups existing in a structure of the polysiloxane-modified polyhydroxypolyurethane resin and a crosslinking agent reactable with the hydroxylgroups.
 21. A weather strip material for coating and/or impregnating ahigh-molecular elastomer material to form a surface treatment layer at aslide contact portion to be brought into sliding contact with anotherpart, comprising a resin composition which comprises thepolysiloxane-modified polyhydroxy polyurethane resin according toclaim
 1. 22. The weather strip material according to claim 21, whereinthe resin composition comprises the polysiloxane-modified polyhydroxypolyurethane resin and a diorganopolysiloxane, which has an averagepolymerization degree of from 5,000 to 100,000, and/or a silicone oil,which has a viscosity of from 100 to 1,000 cs, added in a proportion offrom 1 to 100 parts by mass per 100 parts by mass of thepolysiloxane-modified polyhydroxy polyurethane resin.
 23. The weatherstrip material according to claim 21, wherein the resin compositioncomprises, as a matting agent, a material composed of one fine powder ora combination of two or more fine powders selected from organic finepowders and inorganic fine powders and added in a proportion of from 1to 150 parts by mass per 100 parts by mass of the polysiloxane-modifiedpolyhydroxy polyurethane resin.
 24. The weather strip material accordingto claim 21, wherein the resin composition further comprises a binderresin other than the polysiloxane-modified polyhydroxy polyurethaneresin.
 25. A weather strip comprising a high-molecular elastomermaterial and the weather strip material according to claim 21 coated onand/or impregnated in the high-molecular elastomer material to form asurface treatment layer at a slide contact portion to be brought intosliding contact with another part, wherein the surface treatment layerhas been crosslinked with a crosslinking agent reactable with hydroxylgroups in a structure of the polysiloxane-modified polyhydroxypolyurethane resin in the weather strip material.